Science of synthesis: Houben-Weyl methods of molecular transformations 33 = Category 4, Compounds with two carbon-heteroatom bonds Ene-X compounds (X=S, Se, Te, N, P)
Saved in:
| Main Author: | |
|---|---|
| Other Authors: | |
| Format: | Book |
| Language: | English |
| Published: |
Stuttgart [u.a.]
Thieme
2007
|
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XLII, 866 Seiten Illustrationen 26 cm |
| ISBN: | 9783131188519 9781588904645 |
Staff View
MARC
| LEADER | 00000nam a2200000 cc4500 | ||
|---|---|---|---|
| 001 | BV022192525 | ||
| 003 | DE-604 | ||
| 005 | 20240614 | ||
| 007 | t | ||
| 008 | 061213s2007 a||| |||| 00||| eng d | ||
| 020 | |a 9783131188519 |9 978-3-13-118851-9 | ||
| 020 | |a 9781588904645 |9 978-1-58890-464-5 | ||
| 035 | |a (OCoLC)634509815 | ||
| 035 | |a (DE-599)BVBBV022192525 | ||
| 040 | |a DE-604 |b ger |e rda | ||
| 041 | 0 | |a eng | |
| 049 | |a DE-355 |a DE-20 |a DE-210 |a DE-19 |a DE-91G |a DE-188 |a DE-11 | ||
| 084 | |a VK 7200 |0 (DE-625)147417:253 |2 rvk | ||
| 100 | 1 | |a Abramite, J. A. |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a Science of synthesis |b Houben-Weyl methods of molecular transformations |n 33 = Category 4, Compounds with two carbon-heteroatom bonds |p Ene-X compounds (X=S, Se, Te, N, P) |c ed. board: D. Bellus ... |
| 264 | 1 | |a Stuttgart [u.a.] |b Thieme |c 2007 | |
| 300 | |a XLII, 866 Seiten |b Illustrationen |c 26 cm | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 650 | 0 | 7 | |a Organische Synthese |0 (DE-588)4075695-6 |2 gnd |9 rswk-swf |
| 650 | 0 | 7 | |a Heteroatomare Verbindungen |0 (DE-588)4352909-4 |2 gnd |9 rswk-swf |
| 689 | 0 | 0 | |a Heteroatomare Verbindungen |0 (DE-588)4352909-4 |D s |
| 689 | 0 | 1 | |a Organische Synthese |0 (DE-588)4075695-6 |D s |
| 689 | 0 | |5 DE-604 | |
| 700 | 1 | |a Bellus, Daniel |e Sonstige |4 oth | |
| 700 | 1 | |a Molander, Gary A. |d 1953- |0 (DE-588)1203386230 |4 edt | |
| 700 | 1 | |a Houben, Josef |d 1875-1940 |e Sonstige |0 (DE-588)117013870 |4 oth | |
| 773 | 0 | 8 | |w (DE-604)BV013247070 |g 33 |
| 776 | 0 | 8 | |i Erscheint auch als |n Online-Ausgabe |z 978-3-13-183871-1 |
| 856 | 4 | 2 | |m HBZ Datenaustausch |q application/pdf |u http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015404077&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |3 Inhaltsverzeichnis |
| 943 | 1 | |a oai:aleph.bib-bvb.de:BVB01-015404077 | |
Record in the Search Index
| _version_ | 1807863419566555136 |
|---|---|
| adam_text |
XIII
Table of Contents
Introduction
G. A. Molander
Introduction 1
33.1 Product Class 1: Alk 1 enyl Sulfur Compounds
33.1.1 Product Subclass 1: Alk 1 enesulfonic Acids and Derivatives
J. C. Carretero and R. C. Arrayas
33.1.1 Product Subclass 1: Alk 1 enesulfonic Acids and Derivatives 13
33.1.1.1 Synthesis of Product Subclass 1 13
33.1.1.1.1 Method 1: Synthesis from 2 Chloroalkanesulfonic Acid Derivatives 13
33.1.1.1.2 Method 2: Condensations of the Carbanions of Sulfonic Acid Derivatives
with Carbonyl Compounds 14
33.1.1.1.2.1 Variation 1: Aldol Type Condensations and Related Processes 14
33.1.1.1.2.2 Variation 2: Wadsworth Emmons Alkenation Reactions 15
33.1.1.1.3 Method 3: Cyclic Alk 1 enesulfonic Esters and Sulfonamides by
Metathesis Reactions 16
33.1.1.1.4 Methods 4: Miscellaneous Syntheses of Alk 1 enesulfonic Acid Derivatives
from Other Sulfur Compounds 17
33.1.2 Product Subclass 2: Alk 1 enyl Sulfones
J. C. Carretero and R. C. Arrayas
33.1.2 Product Subclass 2: Alk 1 enyl Sulfones 19
33.1.2.1 Synthesis of Product Subclass 2 19
33.1.2.1.1 Method 1: Sulfonylation of Nucleophilic Alkenyl Reagents 19
33.1.2.1.2 Method 2: Condensation of Sulfonyl Carbanions with
Carbonyl Compounds 20
33.1.2.1.2.1 Variation 1: Aldol Type Condensation and Dehydration 20
33.1.2.1.2.2 Variation 2: Knoevenagel Condensation of Activated Sulfones 22
33.1.2.1.2.3 Variation 3: Condensation of Sulfinyl(sulfonyl)methanes with Aldehydes 23
33.1.2.1.2.4 Variation 4: Horner Wadsworth Emmons Alkenation of
a Sulfonyl Phosphonates 24
33.1.2.1.2.5 Variation 5: Peterson Alkenation of a Silylalkyl Sulfones 26
33.1.2.1.3 Method 3: Sulfonylation of Alkenes Followed by Elimination 28
33.1.2.1.3.1 Variation 1: Chlorosulfenylation of Alkenes, Followed by Sulfur Oxidation
and Elimination 28
33.1.2.1.3.2 Variation 2: Sulfonomercuration of Alkenes Followed by Demercuration 29
33.1.2.1.3.3 Variation 3: Selenosulfonylation of Alkenes Followed by
Selenium Oxidation 30
XIV Table of Contents
33.1.2.1.3.4 Variation 4: lodosulfonylation of Alkenes Followed by Dehydroiodination 31
33.1.2.1.4 Method 4: Sulfonylation of Alkynes 33
33.1.2.1.5 Method 5: Functionalization of Alk 1 ynyl Sulfones 34
33.1.2.1.5.1 Variation 1: Addition Reactions 35
33.1.2.1.5.2 Variation 2: Cycloaddition Reactions 37
33.1.2.1.6 Method 6: Oxidation of Alk 1 enyl Sulfides and Sulfoxides 37
33.1.2.1.7 Method 7: Functionalization of Allyl Sulfones and Derivatives 38
33.1.2.1.8 Method 8: Functionalization of Simple Alk 1 enyl Sulfones 40
33.1.2.1.8.1 Variation 1: a Functionalization 40
33.1.2.1.8.2 Variation 2: Heck Reaction 42
33.1.2.1.8.3 Variation 3: Cross Metathesis Reactions 43
33.1.2.1.8.4 Variation 4: Diels Alder Reactions of Dienyl Sulfones 44
33.1.2.1.8.5 Variation 5: Substitution of P Functionalized Alk 1 enyl Sulfones 45
33.1.3 Product Subclass 3: S Alk 1 enylsulfoximides
J. C. Carretero and R. G. Arrayas
33.1.3 Product Subclass 3: S Alk 1 enylsulfoximides 51
33.1.3.1 Synthesis of Product Subclass 3 51
33.1.3.1.1 Method 1: Condensation of Sulfonimidoyl Carbanions with
Carbonyl Compounds 51
33.1.3.1.1.1 Variation 1: Aldol Type Condensations of a Sulfonimidoyl Carbanions and
the Dehydration of the Intermediate P Hydroxylated Sulfox
imides 52
33.1.3.1.1.2 Variation 2: Peterson and Wadsworth Emmons Alkenation Reactions • • • • 54
33.1.3.1.2 Method 2: Imination of Alk 1 enyl Sulfoxides 55
33.1.3.1.3 Method 3: Functionalization of Simple S Alk 1 enyl and
S Alk 2 enylsulfoximides 56
33.1.4 Product Subclass 4: Alk 1 enesurfinic Acids and Derivatives
J. C. Carretero and R. G. Arrayas
33.1.4 Product Subclass 4: Alk 1 enesurfinic Acids and Derivatives 59
33.1.4.1 Synthesis of Product Subclass 4 59
33.1.4.1.1 Method 1: Reaction of Allenes and Alkynes with Sulfur Dioxide 59
33.1.4.1.2 Method 2: Oxidative Fragmentation of Alk 1 enyl Benzyl Sulfoxides 60
33.1.4.1.3 Method 3: S Oxidation of lsothiazol 3(2H) ones 61
33.1.5 Product Subclass 5: Alk 1 enyl Sulfoxides, Sulfimides,
and Related Compounds
J. C. Carretero and R. G. Arrayas
33.1.5 Product Subclass 5: Alk 1 enyl Sulfoxides, Sulfimides,
and Related Compounds 65
33.1.5.1 Synthesis of Product Subclass 5 66
Table of Contents XV
33.1.5.1.1 Method 1: Sulfinylation of Nucleophilic Alkenyl Reagents 66
33.1.5.1.1.1 Variation 1: Sulfinylation with Menthyl 4 Toluenesulfinate 66
33.1.5.1.1.2 Variation 2: Sulfinylation with Other Enantiopure Sulfinylating Reagents 67
33.1.5.1.2 Method 2: Condensations of Sulfinyl Carbanions (and Related Species)
with Carbonyl Compounds 69
33.1.5.1.2.1 Variation!: Aldol Type Condensations and Dehydrations 69
33.1.5.1.2.2 Variation 2: Mannich Type Reactions 72
33.1.5.1.2.3 Variation 3: Knoevenagel Type Condensations 73
33.1.5.1.2.4 Variation 4: Wadsworth Emmons Alkenation 75
33.1.5.1.2.5 Variation 5: Wittig and Horner Wittig Reactions 79
33.1.5.1.2.6 Variation 6: Peterson Alkenation 80
33.1.5.1.3 Method 3: Conversions of Alkynes into Alkenyl and Allenyl Sulfoxides ••• 81
33.1.5.1.3.1 Variation 1: Additions of Sulfenic Acids to Alkynes 82
33.1.5.1.3.2 Variation 2: Reactions of Sulfenyl Chlorides with Propargylic Alcohols — 83
33.1.5.1.4 Method 4: Addition Reactions to Alkynyl Sulfoxides 84
33.1.5.1.5 Method 5: Oxidation of Alkenyl Sulfides 86
33.1.5.1.6 Method 6: Functionalization of Alkenyl Sulfoxides and Derivatives 88
33.1.5.1.6.1 Variation 1: a Functionalization 88
33.1.5.1.6.2 Variation 2: The Heck Reaction 90
33.1.5.1.6.3 Variation 3: The Stille and Other Palladium Catalyzed
Cross Coupling Reactions 92
33.1.5.1.6.4 Variation 4: Synthesis from Other Alkenyl Sulfoxides 93
33.1.6 Product Subclass 6: Alk 1 enethiols
J. Drabowicz, P. Kietbasinski, and M. Mikotajczyk
33.1.6 Product Subclass 6: Alk 1 enethiols 101
33.1.6.1 Synthesis of Product Subclass 6 101
33.1.6.1.1 Methodi: Reaction of Alkenes with Elemental Sulfur 101
33.1.6.1.2 Method 2: C S Bond Cleavage of Alkenyl Sulfides 101
33.1.6.1.3 Method 3: Reaction of f Alkenyl(phenyl) X3 iodanes with Thioamides 102
33.1.6.1.4 Method 4: Reaction of Haloalkenes with Hydrogen Sulfide 102
33.1.6.1.5 Method 5: Retro Diels Alder Reactions of 9,10 Ethano
9,10 dihydroanthracene 11 thiols 103
33.1.6.1.6 Method 6: Pyrolysis of 1,2 EthanedithiolorThiirane 103
33.1.6.1.7 Method 7: Addition of Hydrogen Sulfide to Alkynes 103
33.1.6.1.8 Method 8: Enethiolization of Thiocarbonyl Compounds 104
33.1.7 Product Subclass 7: Metal Alk 1 enethiolates
J. Drabowicz, P. Kietbasinski, and M. MikoJajczyk
33.1.7 Product Subclass 7: Metal Alk 1 enethiolates 109
33.1.7.1 Synthesis of Product Subclass 7 109
33.1.7.1.1 Methodi: Alkali Metal Cleavage of Alk 1 enyl Alkyl Sulfides 109
33.1.7.1.2 Method 2: Hydrolysis of Alk 1 enyl Thiolacetates 109
XVI Table of Contents
33.1.7.1.3 Method 3: Transformations of Thiiranes and Thiirane 5 Oxides 110
33.1.7.1.4 Method4: Deprotonation of Thiocarbonyl Compounds Ill
33.1.8 Product Subclass 8: Alk 1 enyl Sulfides
J. Drabowicz, P. Kietbasiriski, and M. Mikotajczyk
33.1.8 Product Subclass 8: Alk 1 enyl Sulfides 113
33.1.8.1 Synthesis of Product Subclass 8 113
33.1.8.1.1 Synthesis of Acyclic Alk 1 enyl Sulfides 113
33.1.8.1.1.1 Method 1: Alkylation of Alk 1 enethiolates 113
33.1.8.1.1.2 Method 2: Transformations of 1 Haloalkenes and Their Analogues 114
33.1.8.1.1.2.1 Variation 1: Nucleophilic Substitution by Thiolate Anions and
Their Analogues 114
33.1.8.1.1.2.2 Variation 2: Reactions of 1 Bromoalkenes with Trialkylstannyl Sulfides ••• 115
33.1.8.1.1.2.3 Variation 3: Reactions with Copper Thiolates 116
33.1.8.1.1.2.4 Variation 4: Palladium Catalyzed Reactions with Thiolanes and
Their Equivalents 116
33.1.8.1.1.2.5 Variation 5: Photochemical Reactions between 1 Bromoalk 1 enes and
Sulfides 119
33.1.8.1.1.2.6 Variation 6: Using Alk 1 enylmercury(ll) Halides 119
33.1.8.1.1.2.7 Variation?: Using Alk 1 enyltributylstannanes 120
33.1.8.1.1.2.8 Variation 8: Using (Trimethylsiloxy)alkenes •• 121
33.1.8.1.1.3 Method 3: Syntheses from Alkyl Sulfides 121
33.1.8.1.1.3.1 Variation 1: Dehydrohalogenation of Haloalkyl Sulfides 121
33.1.8.1.1.3.2 Variation 2: Manganese(IV) Oxide Promoted Reactions of Sulfides with
Acetyl Chloride 125
33.1.8.1.1.3.3 Variation 3: Peterson Reactions of a Silyl Derivatives 125
33.1.8.1.1.3.4 Variation 4: Decarboxylation of 2 (Methylsulfanyl)propanoic Acid 127
33.1.8.1.1.4 Method 4: Syntheses from Dithioacetals and Trithioorthoformates 128
33.1.8.1.1.4.1 Variation 1: Reactions with Sulfenyl Chlorides 128
33.1.8.1.1.4.2 Variation 2: Copper or Lewis Acid Mediated Cleavages of Sulfides 129
33.1.8.1.1.4.3 Variation 3: Stereoselective Reduction of Ketene Dithioacetals 129
33.1.8.1.1.4.4 Variation 4: Phosphite Mediated Elimination Reactions 130
33.1.8.1.1.4.5 Variation 5: From Trithioorthoformates 130
33.1.8.1.1.5 Method 5: Aldol Condensations of Sulfides Bearing an
Electron Withdrawing a Substituent 131
33.1.8.1.1.6 Method 6: Syntheses via Organophosphorus Reagents 131
33.1.8.1.1.6.1 Variation 1: From Phosphorus Ylides 131
33.1.8.1.1.6.2 Variation 2: Wadsworth Emmons Horner Reactions 132
33.1.8.1.1.7 Method 7: Synthesis from Alkyl Sulfoxides 134
33.1.8.1.1.7.1 Variation 1: Pummerer Type Rearrangement of ct Chloroalkyl Sulfoxides 134
33.1.8.1.1.7.2 Variation 2: lodotrimethylsilane lnduced Elimination Deoxygenation of
Sulfoxides 135
33.1.8.1.1.8 Method 8: Deoxygenation of Alk 1 enyl Sulfoxides 135
33.1.8.1.1.9 Method 9: Synthesis from Alkynyl Sulfides 136
33.1.8.1.1.9.1 Variation 1: Reduction of Alkynyl Sulfides 136
Table of Contents XVII
33.1.8.1.1.9.2 Variation 2: Hydroboration of Alkynyl Sulfides 137
33.1.8.1.1.9.3 Variation 3: Tantalum Mediated Additions to Alkynyl Sulfides 137
33.1.8.1.1.9.4 Variation 4: Stereoselective Addition of Grignard Reagents to
Alkynyl Sulfides 138
33.1.8.1.1.9.5 Variation 5: Addition of Organocopper Reagents to Alkynyl Sulfides 138
33.1.8.1.1.10 Method 10: Addition of Thiols or Their Derivatives to Alkynes 139
33.1.8.1.1.10.1 Variation 1: Free Radical Additions 139
33.1.8.1.1.10.2 Variation 2: Addition of Thiolates to Alkynes 141
33.1.8.1.1.10.3 Variation 3: Metal Catalyzed Addition of Thiols and Their
Borabicyclo Derivatives to Alkynes 143
33.1.8.1.1.10.4 Variation 4: Addition of Sulfenyl Halides or Sulfenamides to Alkynes 147
33.1.8.1.1.11 Method 11: Ring Opening of Epoxy Sulfides 149
33.1.8.1.1.12 Method 12: Reaction of Benzyne with Thiiranes 151
33.1.8.1.1.13 Method 13: Reaction of N Tosylsulfimides with Potassium tert Butoxide 151
33.1.8.1.2 Synthesis of Cyclic Alk 1 enyl Sulfides 151
33.1.8.1.2.1 Method 1: Reaction of Chlorotropylium Salts with Thiols 152
33.1.8.1.2.2 Method 2: Alkylation of Cycloalk 1 ene 1 thiolates 152
33.1.8.1.2.3 Method 3: Dehydrochlorination of Cyclic Sulfides 152
33.1.8.1.2.3.1 Variation 1: Chlorosulfenylation Dehydrochlorination of Cycloalkenes ¦¦• 152
33.1.8.1.2.3.2 Variation 2: Addition of Thiols to Cycloalk 2 enones, Followed by
Chlorination Dehydrochlorination of the Adducts 153
33.1.8.1.2.4 Method 4: Synthesis from Cycloalkanones and Dithioacetals or Thiols 154
33.1.8.1.2.5 Method 5: Pummerer Reaction of Cyclic Sulfoxides 155
33.1.8.1.2.6 Method 6: Intramolecular Cyclization of Sulfines Derived from
S Unsaturated Dithioesters 156
33.1.8.1.2.7 Method 7: Intramolecular Trapping Reactions of Enethiols
Functionalized by a Silyl Croup 157
33.1.8.1.3 Synthesis of Polyenyl Sulfides 157
33.1.8.1.3.1 Method 1: Sulfanylbuta 1,3 dienes via Elimination Reactions 157
33.1.8.1.3.1.1 Variation 1: Elimination of a Thiol from Bis(dithioacetals) 157
33.1.8.1.3.1.2 Variation 2: Removal of Methanol from Aryl 4,4 Dimethoxybut 2 enyl
Sulfides 158
33.1.8.1.3.1.3 Variation 3: Extrusion of Sulfur Dioxide from 3 Sulfanyl 2,5 dihydro
thiophene 1,1 Dioxides 160
33.1.8.1.3.1.4 Variation 4: Flash Vacuum Pyrolysis of Sulfur Containing Cyclic Derivatives 160
33.1.8.1.3.1.5 Variation 5: Elimination Reactions of Aryl 2 Chlorobut 3 enyl Sulfides ••• 161
33.1.8.1.3.1.6 Variation 6: Elimination Reactions of 2 Methyl 4 sulfanylbut 3 en 2 ols 161
33.1.8.1.3.2 Method 2: Addition of Thiols to But 1 en 3 ynes 162
33.1.8.1.3.3 Method3: Reduction of (1£) But 1 en 3 ynyl Ethyl Sulfides 163
33.1.8.1.3.4 Method 4: Base Catalyzed Ring Opening Reactions of
Sulfur Containing Heterocycles 163
33.1.8.1.3.5 Method 5: Horner Wittig Reaction of Alkenyl Phosphine Oxides
Functionalized with a Phenylsulfanyl Substituent 165
XVIII Table of Contents „„.
33.1.9 Product Subclass 9: Alk 1 enylsulfonium Salts
J. Drabowicz, P. Kietbasiriski, and M. Mikotajczyk
33.1.9 Product Subclass 9: Alk 1 enylsulfonium Salts 169
33.1.9.1 Synthesis of Product Subclass 9 169
33.1.9.1.1 Method 1: Dehydrohalogenation of (2 Haloalkyl)sulfonium Salts 169
33.1.9.1.2 Method 2: S Alkylation of Alk 1 enyl Sulfides 172
33.1.9.1.3 Method 3: Synthesis from Dithioacetals 173
33.1.9.1.4 Method 4: Synthesis from Alkenes 173
33.1.9.1.5 Method 5: Synthesis from Sulfonium Ylides Stabilized by
a Phosphoryl Substituent 174
33.1.10 Product Subclass 10: Alk 1 enesulfenic Acid Derivatives
J. Drabowicz, P. Kietbasinski, and M. Mikotajczyk
33.1.10 Product Subclass 10: Alk 1 enesulfenic Acid Derivatives 177
33.1.10.1 Synthesis of Product Subclass 10 177
33.1.10.1.1 Method 1: Alk 1 enesulfenyl Chlorides by Chlorination of Enethiols or
Alk 1 enyl Sulfides 177
33.1.10.1.2 Method 2: Alk 1 enesulfenyl Chlorides from Allenes and Sulfur Dichloride 178
33.1.10.1.3 Method 3: Alk 1 enesulfenyl Chlorides from Alkynes and
Sulfur Dichloride 178
33.1.10.1.4 Method 4: Alkenesulfenamides by Addition of Amidosulfenyl Chlorides
to Alkynes 179
33.1.10.1.5 Methods: Alk 1 enesulfenamides from Alk 1 enesulfenate Anions 180
33.1.10.1.6 Method 6: Alk 1 enesulfenic Acids by the Enethiolization of Sulfines •••• 181
33.1.11 Product Subclass 11: Alk 1 enyl Disulfides
J. Drabowicz, P. Kiefbasiriski, and M. Mikolajczyk
33.1.11 Product Subclass 11: Alk 1 enyl Disulfides 183
33.1.11.1 Synthesis of Product Subclass 11 183
33.1.11.1.1 Method 1: Sulfenylation of Alkenethiolate Anions 183
33.1.11.1.2 Method 2: Addition of Nucleophiles to Sulfines 185
33.1.12 Product Subclass 12: Thietes and Derivatives
E. Block
33.1.12 Product Subclass 12: Thietes and Derivatives 187
33.1.12.1 Synthesis of Product Subclass 12 188
33.1.12.1.1 Synthesis by Ring Closure Reactions 188
33.1.12.1.1.1 Method 1: Reaction of Sulfenes and Ynamines or Ketene O,N Acetals •¦• 188
33.1.12.1.1.2 Method 2: Photocycloaddition of Thiones to Alkynes 189
33.1.12.1.1.3 Method 3: Reaction of a Perfluorinated Alkeneand tert Butanethiol — 190
Table of Contents XIX
33.1.12.1.1.4 Method 4: Electrocyclic Ring Closure of Enethiones 191
33.1.12.1.2 Synthesis by Ring Transformation 191
33.1.12.1.2.1 Method 1: Ring Enlargement of Diazothiiranimines 191
33.1.12.1.2.2 Method 2: Ring Enlargement of Thiirenes 192
33.1.12.1.2.2.1 Variation 1: Reaction of a Sulfonium Ylide with Diphenylthiirene Dioxide 192
33.1.12.1.2.2.2 Variation 2: From an S Methylthiirenium Ion 192
33.1.12.1.2.3 Method 3: Ring Contraction of Thiophene 1,1 Dioxides 192
33.1.12.1.2.4 Method 4: Synthesis from Thiophenones 193
33.1.12.1.3 Elimination Reactions from Thietanes 194
33.1.12.1.3.1 Method 1: Cope and Hofmann Eliminations 194
33.1.12.1.3.2 Method 2: Elimination of a Hydrogen Halide or Ethanol 195
33.M2.1.4 Synthesis by Substituent Modification 197
33.1.12.1.4.1 Substitution of Hydrogen 197
33.1.12.1.4.1.1 Method 1: Addition and Elimination of Halogen 197
33.1.12.1.4.2 Substitution of Halogens 197
33.1.12.1.4.2.1 Method 1: Michael Addition 197
33.1.12.1.4.3 Modification of Substituents 197
33.1.12.1.4.3.1 Method 1: Enolization/Acylation of Thietan 3 one Derivatives 197
33.1.12.1.4.3.2 Method 2: Double Bond Isomerization 198
33.1.12.1.4.3.3 Method 3: Hydrogenation of 2 Methylenethietes 198
33.1.12.1.4.3.4 Method 4: [4+2] and [2 + 2] Cycloadditions of 2 Methylenethietes 198
33.1.12.1.5 Addition Reactions 199
33.1.12.1.5.1 Method 1: S Alkylation Using Methyl Trifluoromethanesulfonate 199
33.1.12.1.5.2 Method 2: S Oxidation Using Monoperoxyphthalic Acid 199
33.1.12.2 Applications of Product Subclass 12 in Organic Synthesis 200
33.1.12.2.1 Method 1: Ring Opening to Propenethial S,5 Dioxides and
Subsequent Cycloaddition or Rearrangement 200
33.1.13 Product Subclass 13: 2,3 Dihydrothiophenes and Derivatives
E. Block
33.1.13 Product Subclass 13: 2,3 Dihydrothiophenes and Derivatives 203
33.1.13.1 Synthesis of Product Subclass 13 204
33.1.13.1.1 Synthesis by Ring Closure Reactions 204
33.1.13.1.1.1 Methodi: Reaction of Zirconacycles with Sulfur Monochloride 204
33.1.13.1.1.2 Method 2: Reaction of 1 (1 Adamantylcarbonylmethyl)pyridinium
Bromide with (Arylmethylene)cyanothioacetamides 204
33.1.13.1.1.3 Method 3: 1,3 Dipolar Cycloaddition of Mesoionic Thiazolium 4 olates
to Nitroalkenes 205
33.1.13.1.1.4 Method 4: Heating Dialk 1 enyl Disulfides 205
33.1.13.1.1.5 Method 5: Enethiolization of co Halothioacylsilanes 206
33.1.13.1.1.6 Method 6: Synthesis from But 3 ynethiols and Derivatives 206
XX Table of Contents
33.1.13.1.1.6.1 Variation 1: Using Base or Hexacarbonylchromium Catalysis 206
33.1.13.1.1.6.2 Variation 2: From Halocyclizations 207
33.1.13.1.1.7 Method 7: Synthesis from 4,4 Dihalobut 3 enethiols 208
33.1.13.1.1.7.1 Variation 1: From 3 (Difluoromethylene) 2 methyl 6 phenylhexane
1 thiol 208
33.1.13.1.1.7.2 Variation 2: From 4,4 Dibromo 3 methylbut 3 ene 1 thiol 208
33.1.13.1.1.8 Method 8: Synthesis from 5 Substituted Pentan 2 ones 208
33.1.13.1.1.8.1 Variation 1: From 5 Sulfanylated Pentan 2 ones or
5 Bromopentan 2 ones 208
33.1.13.1.1.8.2 Variation 2: From O Ethyl S (4 Oxobutyl) Dithiocarbonates 209
33.1.13.1.1.9 Method 9: Intramolecular Michael Additions 210
33.1.13.1.1.10 Method 10: Cyclization of a Phosphonovinyl Radicals 210
33.1.13.1.1.11 Method 11: Base Induced Cyclizations of Alkynyl Benzyl Sulfides 211
33.1.13.1.1.12 Method 12: Intramolecular Wittig Reactions of Thioesters 212
33.1.13.1.1.13 Method 13: Intramolecular Titanocene(ll) Promoted Alkenations of
Thioesters 212
33.1.13.1.1.14 Method 14: Photocyclization of Bis(2 phenylvinyl) Sulfide 213
33.1.13.1.2 Synthesis by Ring Transformation 214
33.1.13.1.2.1 Method 1: Formal Exchange of Ring Members with Retention of Ring Size 214
33.1.13.1.2.2 Method 2: Light Induced Ring Contraction of 1,2 Dithiins 214
33.1.13.1.2.3 Method 3: Electrocyclic Ring Closure of Thionins 215
33.1.13.1.3 Synthesis by the Elimination Reactions of Thiolanes 215
33.1.13.1.3.1 Method 1: Synthesis from 2 Acetoxy and
2 (Benzoyloxy)tetrahydrothiophenes 215
33.1.13.1.3.2 Method 2: Synthesis from 2 or 3 Hydroxy , 3 Bromo ,
or2 (Alkylsulfanyl)tetrahydrothiophenes 216
33.1.13.1.3.3 Method 3: Bamford Stevens Elimination of the Tosylhydrazone of
Dihydrothiophen 3(2H) one 217
33.1.13.1.4 Synthesis by Substituent Modification 218
33.1.13.1.4.1 Substitution of Hydrogen or Metals 218
33.1.13.1.4.1.1 Method 1: Lithiation of 2.3 Dihydrothiophene and Its Reactions with
Electrophiles 218
33.1.13.1.4.1.2 Method 2: Replacement of Tin by Hydroxyalkyl Croups 218
33.1.13.1.4.2 Substitution of Heteroatoms 219
33.1.13.1.4.2.1 Method 1: Nucleophilic Substitutions of 3 Bromo 2,3 dihydrothiophene
1,1 Dioxide 219
33.1.13.1.4.2.2 Method 2: Substitution of a Trifluoromethylsulfonyloxy Group by a Metal 220
33.1.13.1.4.3 Addition Reactions 221
33.1.13.1.4.3.1 Method 1: Reduction of Thiophenes 221
33.1.13.1.4.3.1.1 Variation 1: Birch Reduction 221
33.1.13.1.4.3.1.2 Variation 2: Samarium(ll) Iodide Mediated Double Electrophilic Reduction 221
33.1.13.1.4.3.2 Method 2: Dimerization of 2,3 Dihydrothiophene and Its 1,1 Dioxide ••• 222
33.1.13.1.4.3.3 Method 3: Addition Reactions Involving Thiophene 1 Oxides 223
33.1.13.1.4.3.3.1 Variation 1: Dihydrodiol Formation or Oxidation/Dimerization 223
33.1.13.1.4.3.4 Method 4: Nucleophilic Additions to Thiophene 1 Oxides or 1,1 Dioxides 224
Table of Contents XXI
33.1.13.1.4.3.5 Method 5: Electrophilic Additions toThiophene 1,1 Dioxides 225
33.1.13.1.4.3.6 Method 6: Diels Alder Additions 226
33.1.13.1.4.3.7 Method 7: Ylide Formation 226
33.1.13.1.4.3.8 Method 8: Oxidation of the Sulfur Atom 227
33.1.13.1.4.3.9 Method 9: Sulfilimine Formation 227
33.1.13.1.4.4 Modification of Substituents 228
33.1.13.1.4.4.1 Method 1: Reduction of the Sulfoxide Group 228
33.1.13.1.4.4.2 Method 2: 4,5 Dihydro 2 thienyl 2 Trifluoromethanesulfonate by
Enolization of Thiophen 2(3H) one 228
33.1.13.1.4.4.3 Method 3: Isomerization of 2,5 Dihydrothiophenes 228
33.1.13.1.4.4.4 Method 4: Base Catalyzed Isomerization of 2,5 Dihydrothiophene
1,1 Dioxides 229
33.1.13.2 Applications of Product Subclass 13 in Organic Synthesis 229
33.1.13.2.1 Method 1: Use as a Protecting Croup for Alcohols 229
33.1.13.2.2 Method 2: Nickel Catalyzed Replacement of a Vinylic C S Bond with
a C C Bond 230
33.1.13.2.3 Method 3: Aromatization of 2,3 Dihydrothiophenes 230
33.1.13.2.4 Method 4: Photoisomerism of 2,3 Dihydrothiophenes to
2 Alkylidenetetrahydrothiophenes 230
33.1.13.2.5 Method 5: Conversion of 2,3 Dihydrothiophenes into
6 Oxo 2 thiabicyclo[3.2.0]heptane 4 carboxylic Acids 230
33.1.13.2.6 Method 6: [2+2] Photochemical Cycloadditions to
2,3 Dihydrothiophene 1,1 Dioxide 231
33.1.13.2.7 Method 7: 3,4 Dihydro 2H thiopyrans from 2,3 Dihydrothiophenium
Methylides 232
33.1.14 Product Subclass 14:3,4 Dihydro 2H thiopyrans and Derivatives
E. Block
33.1.14 Product Subclass 14:3,4 Dihydro 2H thiopyrans and Derivatives 235
33.1.14.1 Synthesis of Product Subclass 14 235
33.1.14.1.1 Synthesis by Ring Closure Reactions 235
33.1.14.1.1.1 Method 1: Synthesis from 1,5 Diketones and Hydrogen Sulfide/
Hydrogen Chloride, Phosphorus Pentasulfide,
or Hexamethyldisilathiane 236
33.1.14.1.1.2 Method 2: Synthesis from 1,4 Dien 3 ones and 1 En 4 yn 3 ones by
Michael Addition 237
33.1.14.1.1.3 Method 3: Synthesis from Propenethial 238
33.1.14.1.1.4 Method 4: Synthesis from Propenethial S,S Dioxide 239
33.1.14.1.1.5 Method 5: Synthesis from Other Enethiones 239
33.1.14.1.1.6 Method 6: Synthesis from Benzothietes 242
33.1.14.1.1.7 Method 7: Double Michael Additions of Malonate Anions to
Alk 1 enylAlk 1 ynylSulfones 242
33.1.14.1.1.8 Method 8: Combination of Enones and Two Three Atom Fragments — 243
33.1.14.1.1.9 Method 9: Photolysis of Pent 4 ynethiol 243
XXII Table of Contents
33.1.14.1.1.10 Method 10: Synthesis from (o Halothioacylsilanes 243
33.1.14.1.1.11 Method 11: Synthesis from 3 Methyl 6 sulfanylhexan 2 ones 244
33.1.14.1.1.12 Method 12: Synthesis from a 5,5 Dibromopent 4 enethiol or
a 5,5 Dibromopent 4 enyl Sulfide 244
33.1.14.1.1.13 Method 13: Synthesis from 1 (Arenesulfonyl) 5 iodobut 1 enyl
Methyl Sulfides 244
33.1.14.1.1.14 Method 14: Thermal Rearrangement of Prop 2 ynyl Vinyl Sulfide 245
33.1.14.1.1.15 Method 15: Cope Rearrangement of Thiocarbonyl Compounds 245
33.1.14.1.1.16 Method 16: Electrocyclic Ring Closure of (3£,5Z) 1,1,1,7,7,7 Hexafluoro
3,4,5 tris(trifluoromethyl)hepta 3,5 diene 2 thione 246
33.1.14.1.1.17 Method 17: Cyclization of S Allyl a Phosphonovinyl Radicals 246
33.1.14.1.2 Synthesis by Ring Transformation 247
33.1.14.1.2.1 Method 1: Ring Enlargement of Acyldihydrothiophenes 247
33.1.14.1.2.2 Method 2: Ring Enlargement of 4,5 Dihydrothiophenium and
Thiophenium 1 Methylides 248
33.1.14.1.3 Synthesis from Dihydro and Tetrahydrothiopyrans 248
33.1.14.1.3.1 Method 1: Rearrangement and/or Elimination Reactions 248
33.1.14.1.4 Synthesis by Substituent Modification 250
33.1.14.1.4.1 Substitution of Hydrogen 250
33.1.14.1.4.1.1 Method 1: Lithiation of 3,4 Dihydro 2H thiopyrans, 2H Thiopyrans,
and 4H Thiopyrans 250
33.1.14.1.4.2 Substitution of Metals 250
33.1.14.1.4.2.1 Method 1: Replacement of Lithium by Organostannyl and
Organosilyl Groups 250
33.1.14.1.4.3 Addition Reactions 250
33.1.14.1.4.3.1 Method 1: Dimerization of 3,4 Dihydro 2H thiopyran 250
33.1.14.1.4.3.2 Method 2: Oxidation of the Sulfur Atom 251
33.1.14.1.4.3.3 Method 3: Sulfilimine Formation 251
33.1.14.1.4.4 Modification of Substituents 251
33.1.14.1.4.4.1 Method 1: Enolization of Dihydrothiopyranones 251
33.1.14.1.4.4.2 Method 2: Cationic Interconversion of 4H Thiopyrans into 2H Thiopyrans 252
33.1.14.1.4.4.3 Method 3: Base Induced Conversions of 2H Thiopyrans into
4H Thiopyrans 252
33.1.14.1.4.4.4 Method 4: Photochemical Conversion of a 2H Thiopyran into
a 4H Thiopyran 254
33.1.14.2 Applications of Product Subclass 14 in Organic Synthesis 254
33.1.14.2.1 Method 1: Nickel Catalyzed Replacement of a Vinylic C—S Bond with
a C C Bond 254
33.1.14.2.2 Method 2: Synthesis of Thiopyrylium Salts 255
33.1.14.2.3 Method 3: Synthesis of 4 Methylene 2,6 diphenyl 4H thiopyrans 255
33.1.14.2.4 Method 4: Synthesis of Chiral Auxiliaries for
Corey Chaykovsky Epoxidation 255
33.1.14.2.5 Method 5: Protecting Croup for Alcohols 256
Table of Contents XXIII
33.1.1s Product Subclass 15: 2,3,4,5 Tetrahydrothiepins, Larger Rings,
and Derivatives
E. Block
33.1.1s Product Subclass 15: 2,3,4,5 Tetrahydrothiepins, Larger Rings,
and Derivatives 259
33.1.15.1 Synthesis of Product Subclass 15 259
33.1.15.1.1 Synthesis by Ring Closure Reactions 259
33.1.15.1.1.1 Method 1: Synthesis from 1,6 Bis(acylsilanes) 259
33.1.15.1.1.2 Method 2: Cyclopalladation of Benzyl Methyl Sulfide 259
33.1.15.1.1.3 Method 3: Synthesis from Diphenylthiirene 1,1 Dioxideand
l Cyclohex 1 enylpyrrolidine 260
33.1.15.1.1.4 Method 4: Synthesis from 1 (Arylsulfonyl) 6 halopent 1 enyl
Methyl Sulfides 260
33.1.15.1.1.5 Method 5: Synthesis from co Halothioacylsilanes 260
33.1.15.1.1.6 Method 6: Synthesis of a 1,2 Dihydro 2 benzothiepin by
Cathodic Reduction of a Benzyl Dithiopivaloate 261
33.1.15.1.2 Synthesis by Ring Transformation 262
33.1.15.1.2.1 Method 1: Ring Enlargement of Three Membered Rings 262
33.1.15.1.2.2 Method 2: Ring Enlargement of Five Membered Rings 263
33.1.15.1.2.2.1 Variation 1: Two Carbon Atom Ring Expansion with
Dimethyl Acetylenedicarboxylate 263
33.1.15.1.2.2.2 Variation 2: [2,3] Sigmatropic Rearrangements of Ylides Obtained from
1 [(Ethoxycarbonyl)methyl] 2 ethynylthiacycloalkanes 263
33.1.15.1.2.3 Method 3: Ring Enlargement of Six Membered Rings 264
33.1.15.1.2.3.1 Variation 1: Two Carbon Atom Ring Expansion with
Dimethyl Acetylenedicarboxylate 264
33.1.15.1.2.3.2 Variation 2: Reaction of 6 Acyl 3,6 dihydro 2H thiopyrans with
Zinc/Chlorotrimethylsilane 265
33.1.15.1.2.3.3 Variation 3: [2,3] Sigmatropic Rearrangements of 1 [(Ethoxycarbonyl)
methyl] 2 ethynylthiepane Sulfonium Ylides 265
33.1.15.1.2.3.4 Variation 4: Rearrangement of Bicyclic Sulfonium Ylides 266
33.1.15.1.2.3.5 Variation 5: Pyrolyses of Sulfoxides 266
33.1.15.1.2.4 Method 4: Ring Enlargement of Seven Membered Rings 267
33.1.15.1.2.4.1 Variation 1: [2,3] Sigmatropic Rearrangement of 1 [(Ethoxycarbonyl)
methyl] 2 ethynylthiocane Sulfonium Ylides 267
33.1.15.1.3 Elimination Reactions Leading toThiacyclohept 2 enes, Thiacyclooct 2 enes,
and Related Systems 267
33.1.15.1.3.1 Method 1: Ring Opening Reactions of Thiaoxabicyclo[3.2.1 ]octanes
andThiaoxabicyclo[3.3.1]nonanes 267
33.1.15.1.3.2 Method 2: Pummerer Reactions 269
33.1.15.1.4 Synthesis by Substituent Modification 270
33.1.15.1.4.1 Substitution of Hydrogen 270
33.1.15.1.4.1.1 Method!: Lithiation of 2,3,4,5 Tetrahydrothiepin 1 Oxide 270
33.1.15.1.4.1.2 Method 2: Allylic Bromination of 4,5 Dihydrothiepin 1,1 Dioxide 270
XXIV Table of Contents
33.1.15.1.4.2 Substitution of Metals 270
33.1.15.1.4.2.1 Method 1: Replacement of Lithium by Alkyl and Hydroxyalkyl Croups 270
33.1.15.1.4.3 Addition Reactions 271
33.1.15.1.4.3.1 Method 1: Oxidation of the Sulfur Atom 271
33.2 Product Class 2: Alk 1 enyl Selenium Compounds
D. Avilov and D. Dittmer
33.2 Product Class 2: Alk 1 enyl Selenium Compounds 275
33.2.1 Product Subclass 1: Alk 1 enyl Selenones 275
33.2.1.1 Synthesis of Product Subclass 1 275
33.2.1.1.1 Method 1: Oxidation of Alk 1 enyl Selenides 275
33.2.2 Product Subclass 2: Alk 1 enyl Selenoxides 276
33.2.2.1 Synthesis of Product Subclass 2 276
33.2.2.1.1 Method 1: Oxidation of Alk 1 enyl Selenides 276
33.2.3 Product Subclass 3: Alk 1 eneselenols 277
33.2.3.1 Synthesis of Product Subclass 3 277
33J.3.1.1 Method 1: Reaction of Divinyl Diselenides with Tributyltin Hydride 277
33.2.4 Product Subclass 4: Metal Alk 1 eneselenolates 277
33.2.4.1 Synthesis of Product Subclass 4 278
33.2.4.1.1 Method 1: Reaction of Metal Complexes with 1,2,3 Selenadiazoles 278
33.2.4.1.2 Method 2: Addition of Metal Complexes Containing Selenium Ligands
to Alkynes 279
33.2.4.1.3 Method 3: Exchange of Selenolate Ligands in Metal Complexes 279
33.2.4.1.4 Methods 4: Other Methods 280
33.2.5 Product Subclass 5: Alk 1 enyl Selenides 280
33.2.5.1 Synthesis of Product Subclass 5 281
33J.5.1.1 Method 1: Coupling of Organoselenenyl Halides or Diorgano Diselenides
with Alk 1 enyl Heteroatom Derivatives 281
33.2.5.1.1.1 Variation 1: Reaction of Organoselenenyl Halides with
Alk 1 enylmagnesium Halides 281
33.2.5.1.1.2 Variation 2: Reaction of Areneselenenyl Halides and Related Compounds
with Alk 1 enylzirconocenes 282
33.2.5.1.1.3 Variation 3: Reaction of an Areneselenenyl Halide with Vinylboronic Acids
and Esters 282
33.2.5.1.1.4 Variation 4: Reaction of Areneselenenyl Halides with
Alk 1 enyl(trialkyl)stannanes and Related Reactions 283
33.2.5.1.1.5 Variation 5: Reaction of Areneselenenyl Halides and Related Compounds
with Alk 1 enyllithiums 283
33.2.5.1.2 Method 2: Coupling of Metal Selenides or Metal Alkane or Arene
selenolates with Alk 1 enyl Heteroatom Derivatives and
Related Reactions 283
Table of Contents XXV
33.2.5.1.3 Method 3: Addition Elimination of Organoselenium Compounds to
Alkenes 284
33.2.5.1.3.1 Variation 1: Addition Elimination of Organoselenenyl Halidesand
Related Compounds 285
33.2.5.1.3.2 Variation 2: Addition Elimination of Selenols 285
33.2.5.1.4 Method 4: Wittig, Horner Wadsworth Emmons, and Related Reactions
of Selenium Precursors with Carbonyl Compounds 286
33.2.5.1.5 Method 5: Addition of Selenium Compounds to Alkynes 287
33.2.5.1.5.1 Variation 1: Addition of Selenols 287
33.2.5.1.5.2 Variation 2: Addition of Arene or Alkaneselenenyl Halides,
Selenosulfonates, and Related Compounds 288
33.2.5.1.5.3 Variation 3: Addition of Diselenides 289
33.2.5.1.5.4 Variation 4: Addition of Other Compounds Containing
a Selenium—Heteroatom Bond 290
33.2.5.1.5.5 Variations 5: Other Variations 291
33.2.5.1.6 Method 6: Addition of Selenium Compounds to Allenes 291
33.2.5.1.7 Method 7: Addition to Alk 1 ynylselenium Compounds 291
33.2.5.1.7.1 Variation 1: Addition to Alk 1 ynyl Selenides 291
33.2.5.1.7.2 Variation 2: Addition to Metal Alk 1 yneselenolates 294
33.2.5.1.8 Method 8: Double Bond Shift of Allyl Selenides and Related Reactions 295
33.2.5.1.9 Methods 9: Other Methods 295
33.2.6 Product Subclass 6: Alk 1 enylselenonium Salts 295
33.2.6.1 Synthesis of Product Subclass 6 295
33.2.6.1.1 Method 1: Alkylation of Alken 1 yl Selenides 295
33.2.6.1.2 Method 2: Addition of Nucleophiles to Alk 1 ynylselenonium Salts 296
33.2.7 Product Subclass 7: Alk 1 enyl Polyselenides 296
33.2.7.1 Synthesis of Product Subclass 7 296
33.2.7.1.1 Method 1: Oxidation of Metal Alk 1 eneselenolates 297
333 Product Class 3: Alk 1 enyl Tellurium Compounds
D. Avilov and D. Dittmer
333 Product Class 3: Alk 1 enyl Tellurium Compounds 303
333.1 Product Subclass 1: Alk 1 enyl /.6 tellanes 303
333.li Synthesis of Product Subclass 1 303
333.1.1.1 Method 1: Substitution of Pentaaryltellurium
Trifluoromethanesulfonates 303
333.2 Product Subclass 2: Alk 1 enyl Telluroxides 304
333.2.1 Synthesis of Product Subclass 2 304
333.2.1.1 Method 1: Addition of Benzenetellurinyl Trifluoromethanesulfonate
to Alkynes 304
333.2.1.2 Method 2: Oxidation of Alk 1 enyl Tellurides 304
333.3 Product Subclass 3: Alk 1 enyl V tellanes 305
XXVI Table of Contents
333.3.1 Synthesis of Product Subclass 3 305
333.3.1.1 Method 1: Metal Tellurium Exchange 305
333.3.1.2 Method 2: Addition of Halogens to Alk 1 enyl Tellurides 305
333.3.1.3 Method 3: Addition of Tellurium(IV) Halides or Organotellurium
TrihalidestoAlkynes 306
333.3.1.4 Method 4: Exchange of Croups on Tellurium in Alk 1 enyl X4 tellanes ¦•• 307
333.3.2 Applications of Product Subclass 3 in Organic Synthesis 308
333.4 Product Subclass 4: Alk 1 enyl Tellurides 308
333.4.1 Synthesis of Product Subclass 4 308
333.4.1.1 Method 1: Coupling of Organotellurenyl Halides or Diorganoditellanes
with Alk 1 enyl Anions or Radical Equivalents 308
333.4.1.1.1 Variation 1: Reaction of Organotellurenyl Halides with Grignard Reagents 309
333.4.1.1.2 Variation 2: Reaction of Organotellurenyl Halides with Alkynylboranes or
Vinylaluminum Compounds 309
333.4.1.1.3 Variation 3: Reaction of Organotellurenyl Halides with
Alk 1 enyl Zirconocenes 310
333.4.1.1.4 Variation 4: Reaction of Organotellurenyl Halides and Derivatives with
Alk 1 enyl Cuprates or Alk 1 enyl Mercury Derivatives 311
333.4.1.1.5 Variation 5: Reaction of 1,2 Bis[(Z) 2 lithiovinyl]benzene Derivatives
and[(1Z,3Z) 1 Lithio 4 (2 lithiophenyl)buta 1,3 dienyl]
(trimethyl)silane with Tellurium Tetrachloride 312
333.4.1.1.6 Variation 6: Intramolecular Baylis Hillman Reactions of
Organotellurenyl Bromides 313
333.4.1.2 Method 2: Alkylation of Alk 1 enyltelluride Anions 313
333.4.1.3 Method 3: Displacement Reactions on Alk 1 enyl Derivatives by
Telluride Anions 314
333.4.1.4 Method 4: Wittig and Related Reactions 315
333.4.1.5 Method 5: Addition of Tellurium Compounds to Alkynes or Allenes 316
333.4.1.5.1 Variations Addition of Tellurols and Metal Tellurides 316
333.4.1.5.2 Variation 2: Addition of Organotellurenyl Halides and Amides 318
333.4.1.5.3 Variation 3: Free Radical Additions of Tellurium Species 319
333.4.1.5.4 Variation 4: Addition of Iron Telluride Complexes 320
333.4.1.6 Method 6: Reductions of Tellurium Compounds 320
333.4.1.6.1 Variations Reduction of Alk 1 enyl Telluroxides 320
333.4.1.6.2 Variation 2: Reduction of Alk 1 enyltellurium Halides 321
333.4.1.6.3 Variation 3: Reduction of Alk 1 enylditellanes 322
333.4.1.6.4 Variation 4: Reduction of Alkynyl Tellurides 322
333.4.1.7 Method 7: Additions to Alkynyl Tellurides 322
333.4.1.8 Method 8: Modifications of Existing Alk 1 enyl Tellurium Species 323
333.4.1.8.1 Variation 1: Addition Reactions to the C=C Bond of Alk 1 enyl Tellurides 323
333.4.1.8.2 Variation 2: Replacement or Modification of Substituents on
the C=C Bond of Alk 1 enyl Tellurides 324
333.4.1.9 Methods 9: Other Methods 326
333.4.2 Applications of Product Subclass 4 in Organic Synthesis 327
333.5 Product Subclass 5: Alk 1 enyltelluronium Salts 328
333.5.1 Synthesis of Product Subclass 5 328
Table of Contents XXVII
333.5.1.1 Method 1: Alkylation of Alk 1 enyl Tellurides 328
333.5.1.2 Method 2: Displacement of Stannanes, Boronic Acids,
and lodophenyl Croups 328
333.6 Product Subclass 6: Dialk 1 enylditellanes 329
333.6.1 Synthesis of Product Subclass 5 329
333.6.1.1 Method 1: Oxidation of Alk 1 enyl Metal Tellurides 329
333.6.1.2 Methods 2: Other Methods 329
33.4 Product Class 4: Alk 1 enyl Nitrogen Compounds
33.4.1 Product Subclass 1:1 Nitroalkenes
N. Ono
33.4.1 ProductSubclass1:1 Nitroalkenes 337
33.4.1.1 Synthesis of Product Subclass 1 337
33.4.1.1.1 Methodi: Nitration of Alkenes 337
33.4.1.1.1.1 Variation 1: Nitration of Vinylsilanes or Vinylstannanes 342
33.4.1.1.1.2 Variation 2: Nitration of a,p Unsaturated Carboxylic Acids 343
33.4.1.1.2 Method 2: Oxidation of Oximes and Amines 344
33.4.1.1.3 Method 3: Elimination Reactions of P Substituted Nitro Compounds •¦• 345
33.4.1.1.3.1 Variation 1: Dehydration of P Nitro Alcohols 346
33.4.1.1.3.2 Variation 2: Elimination of Acids from P Nitro Esters 350
314.1.1.3.3 Variation 3: Elimination of HX from P Nitro Halides 353
33.4.1.1.3.4 Variation 4: Wittig Type Reaction 354
3^4.1.1.3.5 Variation 5: Elimination from P Nitro Sulfides and Sulfoxides 355
314.1.1.3.6 Variation 6: Elimination from a Nitro Selenoxides and P Nitro Selenoxides 356
33.4.1.1.4 Method 4: Synthesis from a Nitro Ketones 357
33.4.1.1.4.1 Variation 1: Synthesis of P Nitroenamines and P Nitrovinyl Sulfides 359
314.1.1.5 Method 5: Addition Elimination Reactions of Nitroalkenes 360
33.4.1.1.5.1 Variation 1: Using Carbon Nucleophiles 360
33.4.1.1.5.2 Variation 2: Using Heteroatom Nucleophiles 365
33.4.2 Product Subclass 2:1 Nitrosoalkenes
H. U. Reissig and R. Zimmer
33.4.2 Product Subclass 2:1 Nitrosoalkenes 371
33.4.2.1 Synthesis of Product Subclass 2 371
33.4.2.1.1 Methodi: Nitrosation Reactions 371
314.2.1.M Variations Nitrosation of Alkenes 371
314.2.1.1.2 Variation 2: Nitrosation of Alkynes 372
33.4.2.1.1.3 Variation 3: Nitrosation of Allenes 372
314.2.1.2 Method 2: Elimination Reactions 372
33.4.2.1.2.1 Variation 1: Dehydrohalogenation of a Halooximes 372
XXVIII Table of Contents
33.4.2.1.2.2 Variation 2: Elimination of Trialkylsilanol from Silyl Nitronates 373
33.4.2.1.2.3 Variation 3: Elimination of Nitrous Acid 374
33.4.2.1.2.4 Variations Elimination of Sulfuric Acid 374
33.4.2.1.3 Method 3: Thermolysis Reactions 375
33.4.2.1.4 Method 4: Photolysis Reactions 375
33.4.2.1.5 Method 5: Reductions of Nitroalkenes 376
33.4.2.1.5.1 Variation 1: Electrochemical Reduction 376
33.4.2.1.5.2 Variation 2: Reduction with Phosphorus Compounds 376
33.4.2.1.6 Method 6: Oxidation Reactions 377
33.4.2.1.7 Method 7: Ring Opening Reactions 377
33.4.2.1.7.1 Variation 1: From Epoxides 377
33.4.2.1.7.2 Variation 2: From Isoxazoles 378
33.4.2.1.8 Method 8: Isomerization Reactions 378
33.4.2.1.9 Method 9: Skeletal Rearrangement Reactions 379
33.4.2.1.10 Method 10: Alkylations of Oximes 379
33.4.2.1.11 Method 11: Derivatization of Stable Nitrosoalkenes 380
33.4.2.2 Applications of Product Subclass 2 in Organic Synthesis 381
33.4.2.2.1 Method 1: Reactions with Nucleophiles 381
33.4.2.2.2 Method 2: Synthesis of a,p Unsaturated Oximes 382
33.4.2.2.3 Method 3: [4+2] Cycloadditions 383
33.4.2.2.4 Method 4: Electrocyclic Ring Closure Reactions 385
33.4.3 Product Subclass 3: W Alk 1 enyliminosulfur Compounds
H. U. Reissig and R. Zimmer
33.4.3 Product Subclass 3: N Alk 1 enyliminosulfur Compounds 391
33.4.3.1 Synthesis of Product Subclass 3 391
33.4.3.1.1 Method 1: Reaction of P Alkoxy Michael Acceptors with
Sulfoximides and Sulfodiimines 391
33.4.3.1.1.1 Variation 1: Reactions with Sulfoximides 391
33.4.3.1.1.2 Variation 2: Reactions with Sulfodiimines 392
33.4.3.1.2 Method 2: Reaction of Alkynes with Dialkylsulfoxonium Salts 392
33.4.3.1.3 Method 3: Reaction of Ethyl Bromoacetate with Sulfoximides 393
33.4.3.1.4 Method 4: Reaction of 4 Amino 1,2 dihydropyrazol 3 one with
Thionyl Chloride 393
33.4.4 Product Subclass 4: Alk 1 enediazonium Salts, Alkeneazoxy,
and Alkeneazo Compounds
33.4.4 Product Subclass 4: Alk 1 enediazonium Salts, Alkeneazoxy,
and Alkeneazo Compounds 395
Table of Contents XXIX
33.4.5 Product Subclass 5: N Alk 1 enyliminophosphorus Compounds
H. U. Reissig and R. Zimmer
33.4.5 Product Subclass 5: N Alk 1 enyliminophosphorus Compounds 397
33.4.5.1 Synthesis of Product Subclass 5 397
33.4.5.1.1 Method 1: Reactions of P Alkoxy Michael Acceptors with Triphenyl
phosphine Imide 397
33.4.5.1.2 Method 2: Reactions of Azides with Triarylphosphines and
Triorganyl Phosphites 397
33A5.1.2.1 Variation 1: With Triarylphosphines 398
33.4.5.1.2.2 Variation 2: With Triorganyl Phosphites 398
33.4.5.1.3 Method 3: Reactions of Nitriles with Triarylphosphines 399
33.4.5.1.4 Method 4: Reactions of Heterocycles Bearing P Acceptor Substituted
Enamine Moieties with Triarylphosphines 399
33.4.5.1.5 Method 5: Elimination Reactions of (a Azidoalkyl)benzotriazoles 400
33.4.5.2 Applications of Product Subclass 5 in Organic Synthesis 400
33.4.5.2.1 Method 1: Aza Wittig Reactions 400
33.4.5.2.2 Method 2: Synthesis of Heterocycles 401
33.4.6 Product Subclass 6: Enamines
T. Sammakia, J. A. Abramite, and M. F. Sammons
33.4.6 Product Subclass 6: Enamines 405
33A6.1 Synthesis of Product Subclass 6 405
33.4.6.1.1 Method 1: Condensation of a Ketone or Aldehyde with an Amine 405
33.4.6.1.1.1 Variation 1: Via Benzotriazole Aminals 406
33.4.6.1.1.2 Variation 2: Using Azeotropic Removal of Water 408
33.4.6.1.1.3 Variation 3: By the Action of Protic Acid Catalysis 409
33.4.6.1.1.4 Variation 4: By the Action of Molecular Sieves as Catalysts and Desiccants 410
33.4.6.1.1.5 Variation 5: By the Action of Calcium Chloride as a Desiccant 411
33.4.6.1.1.6 Variation 6: Bythe Action of Titanium(IV) Chloride as a Promoter 412
33.4.6.1.1.7 Variation 7: By the Action of Boron Trifluoride Diethyl Ether Complex as
a Catalyst 413
33.4.6.1.2 Method 2: Oxidative Amination 414
33.4.6.1.3 Method 3: Cross Coupling Reactions 415
33.4.6.1.3.1 Variation 1: Of Bromides 416
33.4.6.1.3.2 Variation 2: Of Chlorides 418
33.4.6.1.3.3 Variation 3: OfSulfonates 419
33.4.6.1.4 Method 4: Substitution and Addition Elimination Reactions 420
33.4.6.1.5 Method 5: Elimination of Hydrogen 421
33.4.6.1.5.1 Variation 1: Dehydrogenation 421
33A6.1.5.2 Variation 2: Transfer Dehydrogenation 421
33.4.6.1.6 Method 6: Elimination of a Metal Hydroxide 422
33.4.6.1.7 Method 7: Addition of Hydrogen 422
33.4.6.1.7.1 Variation 1: Reduction of Enamides 422
XXX Table of Contents
33.4.6.1.7.2 Variation 2: Dissolving Metal Reduction of Aromatic Amines 423
334.6.1.8 Method 8: Hydroamination 423
33.4.6.1.9 Method 9: Addition of Organometallic Reagents to Nitriles 426
334.6.1.10 Method 10: Hydroaminomethylation 428
334.6.1.11 Method 11: Isomerization 429
334.6.1.12 Method 12: Wittig Reaction of Amides 432
334.6.1.13 Method 13: Homer Wittig Reaction of Ketones and Aldehydes 433
334.6.1.14 Method 14: Alkylidenation of Carbonyl Croups via Titanium Carbenes ••• 434
334.6.1.14.1 Variation 1: Using Dialkyltitanocenes 435
334.6.1.14.2 Variation 2: Using Tebbe's Reagent 436
33.4.6.1.14.3 Variation 3: Takai Alkylidenation 436
334.6.1.14.4 Variation 4: Alkylidenation of Amides with Thioacetals Using
a Titanium(ll) Complex 437
33.4.7 Product Subclass 7: Enammonium Salts
T. Sammakia, J. A. Abramite, and M. F. Sammons
334.7 Product Subclass 7: Enammonium Salts 443
33.4.7.1 Synthesis of Product Subclass 7 443
33.4.7.1.1 Method 1: Alkylation of Enamines 443
334.7.1.2 Method 2: Conjugate Addition/Elimination 444
33.4.7.1.3 Method 3: Alkylation/Elimination 445
334.7.1.4 Method 4: Copper Catalyzed SN2' Substitution of Propargyl Chlorides •• 445
334.7.1.5 Methods: Elimination of a Hydrogen Halide or Water 446
33.4.7.1.6 Method 6: Addition of Trialkylammonium Salts to Activated Alkynes • • • 447
334.7.1.7 Method 7: Cyclopropyliminium Ion Rearrangement 447
334.8 Product Subclass 8: N Silylenamines
S.J. Collier
334.8 Product Subclass 8: /V Silylenamines 451
334.8.1 Synthesis of Product Subclass 8 453
334.8.1.1 Method 1: Synthesis from Imines 453
334.8.1.1.1 Variation 1: Direct Silylation of Imines or Enamines 453
334.8.1.1.2 Variation 2: Other Approaches Involving Imines 458
334.8.1.2 Method 2: Synthesis from Nitriles 460
334.8.1.2.1 Variation 1: Nucleophilic Attack on Nitriles 460
334.8.1.2.2 Variation 2: Other Approaches Involving Nitriles 466
334.8.1.3 Method 3: Isomerization Reactions 467
334.8.1.4 Methods 4: Miscellaneous Methods 469
Table of Contents XXXI
33.4.9 Product Subclass 9: W Borylenamines
S.J. Collier
33.4.9 Product Subclass 9: JV Borylenamines 475
33.4.9.1 Synthesis of Product Subclass 9 477
33.4.9.1.1 Method 1: Direct Borylation of Imines (or Enamines) 477
33.4.9.1.2 Method 2: Synthesis from 1,2 Azaborolium Salts 480
33.4.9.1.3 Method 3: Synthesis from Other N Borylenamines 481
33.4.9.1.4 Methods 4: Miscellaneous Procedures 483
33.4.10 Product Subclass 10: N Haloenamines
S.J. Collier
33.4.10 Product Subclass 10: Af Haloenamines 487
33.4.10.1 Synthesis of Product Subclass 10 487
33.4.10.1.1 Method 1: Halogenation of Enamides 487
33.4.10.1.2 Method 2: N Halopyridinones and Related Compounds by
Direct Halogenation 488
33.4.11 Product Subclass 11: (V Alk 1 enylhydroxylamines
S.J. Collier
33.4.11 Product Subclass 11: /V Alk 1 enylhydroxylamines 493
33.4.11.1 Synthesis of Product Subclass 11 494
33.4.11.1.1 Method 1: Conjugate Addition Reactions of Hydroxylamines 494
33.4.11.1.1.1 Variations WithAlkenes 494
33.4.11.1.1.2 Variation 2: WithAlkynes 496
33.4.H.1.2 Method 2: Synthesis from Hydroxylamines and Aldehydes or Ketones 498
33.4.11.1.3 Methods 3: Miscellaneous Methods 500
33.4.12 Product Subclass 12: /V Alk 1 enylaminosulfur Compounds
S.J. Collier
33.4.12 Product Subclass 12: /V Alk 1 enylaminosulfur Compounds 503
33.4.12.1 Synthesis of Product Subclass 12 504
33.4.12.1.1 Method 1: Synthesis from Imines and Enamines and
Electrophilic Sulfur Agents 504
33.4.12.1.2 Method 2: Synthesis from N Sulfonylimines and Related Compounds • • • 505
33.4.12.1.2.1 Variation 1: Through Deprotonation and Quenching of /V Sulfanyl and
N Sulfinylimines 505
33A12.1.2.2 Variation 2: Through Nucleophilic Attack on N Sulfonylimines 506
33^.12.1.3 Method 3: Synthesis from Primary and Secondary Sulfonamides 509
33A12.1.4 Method 4: Synthesis through 1,2 Elimination Reactions of Amines 511
33A12.1.5 Method 5: Synthesis through Cross Coupling Reactions 512
XXXH Table of Contents _.
33.4.12.1.6 Method 6: Synthesis by Isomerization and Rearrangement 515
33.4.12.1.7 Methods 7: Miscellaneous Methods 517
33.4.13 Product Subclass 13: Alk 1 enylhydrazines
S.J. Collier and M. D. McLaws
33.4.13 Product Subclass 13: Alk 1 enylhydrazines 521
33.4.13.1 Synthesis of Product Subclass 13 524
33.4.13.1.1 Method 1: Synthesis from Hydrazines and Carbonyl Compounds 524
33.4.13.1.1.1 Variation 1: Monosubstituted or N,N Disubstituted Hydrazines 524
33.4.13.1.1.2 Variation 2: N,N' Disubstituted Hydrazines or Trisubstituted Hydrazines 526
33.4.13.1.2 Method 2: Synthesis by Conjugate Addition 528
33.4.13.1.2.1 Variation 1: Of Hydrazines to Alkynes 528
33.4.13.1.2.2 Variation 2: Of Hydrazines to p Substituted Alkenes 530
33.4.13.1.3 Methods 3: Miscellaneous Methods 534
33.4.14 Product Subclass 14: Alk 1 enyl Azides
S.J. Collier
33.4.14 Product Subclass 14: Alk 1 enyl Azides 541
33.4.14.1 Synthesis of Product Subclass 14 544
33.4.14.1.1 Method 1: Condensation of Arylaldehydes with a Azido Esters 544
33.4.14.1.2 Method 2: 1,2 Elimination Reactions 549
33.4.14.1.3 Method 3: 1,4 Addition Reactions 553
33.4.14.1.4 Methods 4: Miscellaneous Methods 556
33.4.15 Product Subclass 15: A/ Alk 1 enylaminophosphorus Compounds
S.J. Collier
33.4.15 Product Subclass 15: Af Alk 1 enylaminophosphorus Compounds 565
33.4.1S.1 Synthesis of Product Subclass 15 565
33.4.15.1.1 Method 1: Synthesis from Imines or Enamines and
Phosphorus Electrophiles 565
33.4.15.1.2 Method 2: Synthesis from Phosphamides and Aldehydes 567
33.4.15.1.3 Method 3: Synthesis from N AllylphosphoricTriamides 569
33.4.15.1.4 Method 4: Synthesis from Nitriles 571
33.4.15.1.5 Methods 5: Miscellaneous Methods 572
33.4.1 e Product Subclass 16:1,2 Oihydroazetes and Derivatives
P. Jubault, E. Leclerc, and J. C. Quirion
33.4.16 Product Subclass 16:1,2 Dihydroazetes and Derivatives 577
314.16.1 Synthesis of Product Subclass 16 577
33.4.16.1.1 Synthesis by Ring Closure Reactions 577
Table of Contents XXXIII
33.4.16.1.1.1 Method 1: Addition of Amines to a Perfluoroenone 577
33.4.16.1.1.2 Method 2: Addition of Amines to Hexafluoropropene Trimers 578
33.4.16.1.1.3 Method 3: [2 + 2] Cycloaddition between an Imine and a Ketene Aminal 579
33.4.16.1.2 Elimination Reactions from Azetidines 579
33.4.16.1.2.1 Method 1: Elimination of a Methanesulfonate Croup 579
33.4.16.1.2.1.1 Variation 1: Synthesis of N Acyl 1,2 dihydroazetes 579
33.4.16.1.2.1.2 Variation 2: Synthesis of N Mesyl and N Nitro 1,2 dihydroazetes 580
33.4.16.1.2.2 Method 2: 1,2 Photoaromatization Reaction of
an Azabicyclohexane Type Diels Alder Adduct 580
33.4.16.1.3 Synthesis by Substituent Modification 581
33.4.16.1.3.1 Addition Reactions 581
33.4.16.1.3.1.1 Method 1: Addition of Malonate Derivatives to Azetes 581
33.4.17 Product Subclass 17: 2,3 Dihydro 1 H pyrroles and Derivatives
P. Jubault, E. Leclerc, and J. C. Quirion
33.4.17 Product Subclass 17:2.3 Dihydro 1 H pyrroles and Derivatives 583
334.17.1 Synthesis of Product Subclass 17 583
33.4.17.1.1 Synthesis by Ring Closure Reactions 583
33.4.17.1.1.1 Method 1: Addition/Cyclization of Sulfonamide Anions with
AlkynyliodoniumTrifluoromethanesulfonates 583
33.4.17.1.1.2 Method 2: lodocyclization of Alk 3 ynylsulfonamides 584
33.4.17.1.1.3 Method 3: Palladium Catalyzed Cyclization of a Propargyl
a Amino Esters 585
33.4.17.1.1.4 Method 4: Ring Closing Metathesis of N Alk 3 enyl
N alk 1 ynylsulfonamides 585
314.17.1.1.5 Method 5: Ring Closing Metathesis of N Alk 3 enylenamines 586
33.4.17.1.2 Elimination Reactions from Pyrrolidines 587
33.4.17.1.2.1 Method 1: Reduction of Lactams Followed by Elimination 587
33.4.17.1.2.2 Method 2: Dehydration of Pyrrolidin 3 ols 591
33.4.17.1.3 Synthesis by Substituent Modification 592
33.4.17.1.3.1 Method 1: Heck Reactions of 2,3 Dihydropyrroles 592
33.4.17.1.3.2 Method 2: Isomerizing Heck Reactions of 2,5 Dihydropyrroles 593
33.4.17.1.3.3 Method 3: Coupling Reactions of Lactam Derived Alkenyl
Trifluoromethanesulfonates 595
33.4.18 Product Subclass 18:1,2 Dihydropyridines, 1,4 Dihydropyridines,
and Derivatives
J. C. Quirion, E. Leclerc, and P. Jubault
33.4.18 Product Subclass 18:1,2 Dihydropyridines, 1,4 Dihydropyridines,
and Derivatives 601
334.18.1 Synthesis of Product Subclass 18 601
XXXIV Table of Contents _.
33.4.18.1.1 Synthesis by Ring Closure Reactions 601
33.4.18.1.1.1 Method!: Three Component Hantzsch Synthesis 601
33.4.18.1.1.1.1 Variation 1: Classical Hantzsch Reaction 601
33.4.18.1.1.1.2 Variation 2: Microwave Activation 602
33.4.18.1.1.1.3 Variation 3: Miscellaneous Approaches 603
33.4.18.1.1.1.4 Variation 4: Solid Phase Hantzsch Synthesis 604
33.4.18.1.1.2 Method 2: Addition/Cyclization of Nitrogen Nucleophiles to
Dicarbonyl Compounds 605
33.4.18.1.1.2.1 Variation 1: Condensation of Amines with Dialdehydes 605
33.4.18.1.1.2.2 Variation 2: Condensation of Amides with Dialdehydes 606
33.4.18.1.1.2.3 Variation 3: Condensation of Ammonia with 1,5 Diketones 606
33.4.18.1.1.3 Method 3: Aza Diels Alder Reaction of 1 Azadienes 607
33.4.18.1.1.4 Method 4: Asymmetric Two Component Hantzsch Reaction 609
33.4.18.1.1.5 Method 5: 6it Electrocyclization of 1 Azatrienes 610
33.4.18.1.2 Synthesis by Ring Transformation 611
33.4.18.1.2.1 Method 1: Rearrangement of a 3,6,7 Triazatricyclo[3.2.1.02 4]octane
Derivative 611
33.4.18.1.2.2 Method 2: Radical Deoxygenation of 3 Azatricyclo[2.2.1.02 6]
heptan 5 ols 612
33.4.18.1.3 Synthesis by Substituent Modification 612
33.4.18.1.3.1 Addition Reactions 612
33.4.18.1.3.1.1 Method 1: Hydride Reductions 612
33.4.18.1.3.1.2 Method 2: Dissolving Metal Reductions 614
33.4.18.1.3.1.3 Method 3: Dithionite Reductions 615
33.4.18.1.3.1.4 Method 4: Addition of Grignard Reagents 615
33.4.18.1.3.1.5 Method 5: Addition of Organotin Reagents 617
33.4.18.1.3.1.6 Method 6: Addition of Organocopper and Organocuprate Reagents — 618
33.4.18.1.3.1.7 Method 7: Addition of Enolates and Enol Ethers 620
33.4.18.1.3.1.8 Method 8: Addition of Other Carbon Nucleophiles 621
33.4.18.1.3.1.9 Method 9: Asymmetric Addition of Nucleophiles to Pyridinium Salts — 622
33.4.18.1.3.1.9.1 Variation 1: Chirality on the Nitrogen Atom 622
33.4.18.1.3.1.9.2 Variation 2: Addition to Chiral Nicotinic Acid Derivatives 624
33.4.18.1.3.1.9.3 Variation 3: Catalytic Asymmetric Reissert Reaction 625
33.4.19 Product Subclass 19:1,2,3,4 Tetrahydropyridines and Derivatives
J. C. Quirion
33.4.19 Product Subclass 19:1,2,3,4 Tetrahydropyridines and Derivatives 629
33.4.19.1 Synthesis of Product Subclass 19 629
33.4.19.1.1 Synthesis by Ring Closure Reactions 629
33.4.19.1.1.1 Method 1: [4+2] Cycloaddition Reactions of 1 Azabutadienes 630
33.4.19.1.1.1.1 Variation 1: Cyclization of N Acyl 2 cyano 1 azabutadienes 630
33.4.19.U.1.2 Variation 2: Cyclization of N Phenyl 2 cyano 1 azabutadienes 631
33.4.19.1.1.1.3 Variation 3: Cyclization of 2 Cyano N (ethoxycarbonyl) 1 azabutadienes 632
Table of Contents XXXV
33.4.19.1.1.2 Method 2: Photochemical Cycloaddition of 3 Aminopropenals and
Alkenes 632
33.4.19.1.1.3 Method 3: Cyclization/lsomerization of 6 Chloroimines 633
33.4.19.1.1.3.1 Variation 1: In Situ Preparation of 8 Chloroimines 633
33.4.19.1.1.3.2 Variation 2: Cyclization after Isolation of 6 Chloroimines 633
33.4.19.1.1.3.3 Variation 3: Nucleophile lnduced Cyclization of 5 Chloroimines 634
33.4.19.1.1.4 Method 4: Intramolecular Cyclization of Aminoaldehydes and
Derivatives 635
33.4.19.1.1.4.1 Variation 1: Intramolecular Cyclization of AminoAcetals 635
33.4.19.1.1.4.2 Variation 2: Intramolecular Cyclization of an Amide and an Aldehyde or
Acetal 636
33.4.19.UA3 Variation 3: Intramolecular Cyclization of Carbamates and Aldehydes — 637
33.4.19.1.1.4.4 Variation 4: Intramolecular Condensation of Tosylamines and Acetals ••• 638
33.4.19.1.1.5 Method 5: Palladium Induced Intramolecular Cyclization of an
(o Alkenic Tosylamide 639
334.19.1.1.6 Method 6: Transition Metal Catalyzed Cyclization 639
33.4.19.1.1.6.1 Variation 1: Platinium Mediated Cycloisomerization of Ene Ynamides •¦• 639
334.19.1.1.6.2 Variation 2: Ring Closing Metathesis of Ene Ynamides 640
33.4.19.1.1.6.3 Variation 3: Ring Closing Metathesis of Ene Enamides 640
334.19.1.1.7 Method 7: Intramolecular Cyclization of Enamino Esters, Ketones,
or Sulfones 641
334.19.1.1.7.1 Variation 1: Cyclization Involving a Halogen Leaving Group 641
334.19.1.2 Synthesis by Transformation of a Cyclic Substrate 643
334.19.1.2.1 Method 1: Reduction/Elimination of a Lactam 643
334.19.1.2.1.1 Variation 1: Reduction of Unsaturated Lactams 643
334.19.1.2.2 Method 2: Elimination of a Phenylselanyl Group 644
334.19.1.2.3 Method 3: Hydrogenation of Pyridine, Pyridinium Salts,
and Dihydropyridines 644
334.19.1.2.4 Method 4: Hydride Reduction of Pyridines and Dihydropyridines 646
334.19.1.2.5 Method 5: Addition Reactions to 2,3 Dihydropyridinium Salts 647
334.19.1.2.5.1 Variation 1: Addition of Organometallic Compounds 648
334.19.1.2.5.2 Variation 2: Addition of Alcohols, Thiols, and Amines 649
334.19.1.2.5.3 Variation 3: Addition of P Dicarbonyl Anions 650
334.19.1.2.6 Method 6: 2 Carbamoylation of 1,4 Dihydropyridines 650
334.19.1.3 Functionalization of 1,2,3,4 Tetrahydropyridines 651
334.19.1.3.1 Method 1: Carboxymethylation of Substituted
Vinyl Trifluoromethanesulfonates 652
334.19.1.3.2 Method 2: Suzuki Reactions of Vinyl Trifluoromethanesulfonates 653
334.19.1.3.3 Method 3: Functionalization of Boronates 654
334.19.1.3.4 Method 4: Coupling Reactions of Vinyl Phosphates 655
XXXVI Table of Contents
33.4.20 Product Subclass 20: 2,3,4,5 Tetrahydro i H azepines, Larger Rings,
and Derivatives
J. C. Quirion, E. Leclerc, and P. Jubault
33.4.20 Product Subclass 20: 2,3,4,5 Tetrahydro 1 H azepines, Larger Rings,
and Derivatives 659
33.4.20.1 Synthesis of Product Subclass 20 659
33.4.20.1.1 Synthesis by Ring Closure Reactions 659
33.4.20.1.1.1 Method 1: Rhodium Catalyzed Alkene Allene Carbocyclization 659
33.4.20.1.2 Elimination Reactions 660
33.4.20.1.2.1 Method 1: Elimination Reactions of 2 Hydroxyazepanes and Derivatives 660
33.4.20.1.3 Synthesis by Substituent Modification 660
33.4.20.1.3.1 Method 1: Hydrodesulfurization of a Thiolactam Derived Enol Ether — 660
33.4.20.1.3.2 Method 2: Coupling Reactions of Lactam Derived
Vinyl Trifluoromethanesulfonates 661
33.4.20.1.3.3 Method 3: Reduction and Suzuki Coupling Reactions of Lactam Derived
Vinyl Phosphates 662
33.5 Product Class 5: Alk 1 enyl Phosphorus Compounds
33.5.1 Product Subclass 1: Alk 1 enylphosphonic Acids and Derivatives
A. C. Caumont and M. Culea
33.5.1 Product Subclass 1: Alk 1 enylphosphonic Acids and Derivatives 665
33.5.1.1 Synthesis of Product Subclass 1 665
33.5.1.1.1 Method 1: Hydrophosphorylation of Alkynes 665
33.5.1.1.1.1 Variation 1: Metal Catalyzed Hydrophosphorylation 665
33.5.1.1.1.2 Variation 2: Base Catalyzed Hydrophosphorylation 666
333.1.1.2 Method 2: P—C Bond Formation from Dialkyl Phosphonates or
Trialkyl Phosphites and Vinyl Halides 667
33.5.1.1.2.1 Variation 1: Michaelis Arbuzov Type Reaction 668
33.5.1.1.2.2 Variation 2: Metal Catalyzed Reaction of Dialkyl Phosphonates and
Vinyl Halides 668
333.1.1.3 Method 3: Wittig Horner Type Alkenation 669
33.5.1.1.3.1 Variation 1: Deprotonation of Methylenebis(phosphonates) 669
33.5.1.1.3.2 Variation 2: Halogen Lithium Exchange from (Halomethyl)phosphonates 671
33.5.1.1.3.3 Variation 3: Synthesis from (Dialkoxyphosphoryl)phosphoniomethanides 672
33.5.1.1.4 Method 4: Peterson Type Alkenylation 673
333.1.1.4.1 Variation 1: Synthesis from (I Silylalkyl)phosphonates 673
333.1.1.4.2 Variation 2: Synthesis from Alkylphosphonates by In Situ Silylation 673
333.1.1.4.3 Variation 3: Synthesis from Bis silylated Methylphosphonates 674
333.1.1.5 Methods: Other Alkenation Reactions 675
333.1.1.5.1 Variation 1: Synthesis from a Stannylated Carbanions 675
Table of Contents XXXVII
33.5.1.1.5.2 Variation 2: Synthesis from a Sulfinyl Carbanions 676
33.5.1.1.6 Method 6: Knoevenagel Type Reactions 677
33.5.1.1.6.1 Variation 1: Using an Aldehyde and a Base Titanium(IV) Chloride System 677
33.5.1.1.6.2 Variation 2: Using Bis aminals and a Haloacetic Acids 678
33.5.1.1.6.3 Variation 3: Using Aldehydes and Tributylarsine 679
33.5.1.1.7 Method 7: Mannich Type Reaction 679
33.5.1.1.8 Method 8: Oxidative Elimination of Sulfanyl or Selanyl Moieties 680
33.5.1.1.9 Method 9: Elimination from P Heteroatom Substituted
Alkylphosphonates 680
33.5.1.1.9.1 Variation 1: Dehydrohalogenation 680
33.5.1.1.9.2 Variation 2: Dehydration 681
33.5.1.1.9.3 Variation 3: Elimination of Nitrous Acid 681
33.5.1.1.10 Method 10: Hydrogenation of Alk 1 ynylphosphonates 682
33.5.1.1.11 Method 11: 1,4 Addition of Nucleophiles to Alk 1 ynylphosphonates •••• 683
33.5.1.1.12 Method 12: Synthesis from Organometallic Intermediates Generated
from Alk 1 ynylphosphonates 683
33.5.1.1.12.1 Variation 1: Synthesis from (Borylalk i enyl)phosphonates 684
33.5.1.1.12.2 Variation 2: Synthesis from (Phosphorylalk i enyl)copper(l) Compounds 685
33.5.1.1.12.3 Variation 3: Synthesis from (Tellanylalk i enyl)phosphonates 686
333.1.1.12.4 Variation 4: Synthesis from Zirconacyclic and Titanacyclic Phosphonates 686
33.5.1.1.13 Method 13: Modification of the Existing Double Bond in
Alk 1 enylphosphonates 688
33.5.1.1.13.1 Variation 1: Metal Catalyzed Cross Coupling Reactions 689
333.1.1.13.2 Variation 2: Alkene Cross Metathesis 690
333.1.1.14 Method 14: Transformation of Alk 1 enylphosphonates into
the Corresponding Phosphonic Acids 690
333.1.1.14.1 Variation 1: Acidic Hydrolysis 691
333.1.1.14.2 Variation 2: Using Bromotrimethylsilane 691
333.2 Product Subclass 2: Alk 1 enylphosphinic Acids and Derivatives
A. C. Caumont and M. Gulea
333.2 Product Subclass 2: Alk 1 enylphosphinic Acids and Derivatives 695
333.2.1 Synthesis of Product Subclass 2 695
333.2.1.1 Method 1: Hydrophosphinylation of Alkynes 695
333.2.1.2 Method 2: Synthesis from Alkylphosphonochloridoates and
Vinylic Organometallic Compounds 697
333.2.1.3 Method 3: Metal Catalyzed Phosphorus Carbon
Cross Coupling Reactions 697
333.2.1.4 Method 4: Alkenylation Reactions 698
33.5.2.1.5 Method 5: Elimination from P Heteroatom Substituted
Alkylphosphinic Esters 699
XXXVIII Table of Contents
33.5.3 Product Subclass 3: Alk 1 enylphosphine Oxides and Derivatives
A. C. Gaumont and M. Gulea
33.5.3 Product Subclass 3: Alk 1 enylphosphine Oxides and Derivatives 701
33.S.3.1 Synthesis of Product Subclass 3 701
33.5.3.1.1 Method 1: Hydrophosphinylation of Alkynes 701
33.5.3.1.2 Method 2: Metal Catalyzed Phosphorus Carbon
Cross Coupling Reaction 702
33.5.3.1.3 Method 3: Alkenation Reactions 703
33.5.3.1.4 Method 4: Elimination from a Oxygenated Alkylphosphine Oxides 704
33.5.3.1.4.1 Variation 1: From (1 Hydroxyalkyl)phosphine Oxides 704
33.5.3.1.4.2 Variation 2: From (1,2 Epoxyalkyl)phosphine Oxides 704
333.3.1.5 Method 5: Elimination from P Heteroatom Substituted
Alkylphosphine Oxides 705
333.3.1.6 Method 6: Nucleophilic 1,4 Addition to Alk 1 ynylphosphine Oxides — 705
3333.1.7 Method 7: Synthesis from Organometallic Intermediates Generated
from Alk 1 ynylphosphine Oxides 706
333.3.1.8 Method 8: Modification of an Existing Double Bond 707
333.3.1.9 Method 9: Oxidation of Alk 1 enylphosphines 708
33.5.3.1.10 Method 10: Acidic Hydrolysis of P Alk 1 enylphosphinous Amides 709
33.5.4 Product Subclass 4: Alk 1 enylphosphines
A. C. Gaumont and M. Gulea
33.5.4 Product Subclass 4: Alk 1 enylphosphines 711
333.4.1 Synthesis of Product Subclass 4 711
333.4.1.1 Method 1: Hydrophosphination of Alkynes with Primary or
Secondary Phosphines 711
333.4.1.1.1 Variation 1: Hydrophosphination under Basic Conditions 712
333.4.1.1.2 Variation 2: Radical Catalyzed Hydrophosphination 713
33.5.4.1.1.3 Variation 3: Thermal Hydrophosphination 714
333.4.1.1.4 Variation 4: Metal Catalyzed Hydrophosphination 714
333.4.1.2 Method 2: Metal Catalyzed Phosphorus Carbon
Cross Coupling Reactions 716
333.4.1.2.1 Variation 1: Palladium Catalyzed Phosphorus Carbon
Cross Coupling Reactions 716
333.4.1.2.2 Variation 2: Nickel Catalyzed Phosphorus Carbon
Cross Coupling Reactions 718
333.4.1.3 Method 3: Reaction between Halophosphines and
Vinylic Organometallic Derivatives 719
333.4.1.4 Method 4: Reduction of Phosphorus Compounds 720
333.4.1.4.1 Variation 1: Reduction of Phosphonates and Phosphinates 720
333.4.1.4.2 Variation 2: Reduction of Chlorophosphines 721
333.4.1.5 Methods 5: Miscellaneous Methods 722
Table of Contents XXXIX
333.5 Product Subclass 5: Alk 1 enylphosphonium Salts
A. C. Gaumont and M. Culea
33.5.5 Product Subclass 5: Alk 1 enylphosphonium Salts 725
33.5.5.1 Synthesis of Product Subclass 5 725
33.5.5.1.1 Method 1: Alkenylation of Tertiary Phosphines 725
33.5.5.1.1.1 Variation 1: Nucleophilic Addition of Triphenylphosphine to
Activated Alkynes 725
33.5.5.1.1.2 Variation 2: Metal Catalyzed Addition of Triphenylphosphine to Alkynes 726
33.5.5.1.2 Method 2: Modification of Phosphoranes or Phosphonium Salts 727
33.5.5.1.2.1 Variation 1: Addition Elimination Reactions of Phosphoranes 727
33.5.5.1.2.2 Variation 2: Elimination Addition from Vinylidene Bisphosphonium Salts 727
335.5.1.3 Methods 3: Miscellaneous Methods 728
33.5.6 Product Subclass 6: P Heteroatom Substituted Alk 1 enylphosphines
A. C. Gaumont and M. Gulea
33.5.6 Product Subclass 6: P Heteroatom Substituted Alk 1 enylphosphines ¦¦• 731
335.6.1 Synthesis of Product Subclass 6 731
335.6.1.1 Method 1: Alk 1 enyl(amino)phosphines by Vinylation of
Halophosphines 731
33.5.6.1.1.1 Variation 1: Synthesis from Amino(chloro)phosphines 731
335.6.1.1.2 Variation 2: Synthesis from Amino(chloro)phosphines Generated In Situ 732
335.6.1.2 Method 2: Alk 1 enylphosphonous Diamides by Reaction between
Enamines, Phosphorus Trihalides, and Amines 733
335.6.1.3 Method 3: Alk 1 enylphosphonous Dihalides by the Reaction of
Phosphorus Trihalides and Organometallic Derivatives 734
335.6.1.4 Method 4: Alk 1 enyl(halo)phosphines by the Reaction of
Tungsten Phosphinidene Complexes and Chloroalkenes — 734
335.7 Product Subclass 7:1,2 Dihydrophosphetes and Derivatives
Gy. Keglevich and H. Szelke
33.5.7 Product Subclass 7:1,2 Dihydrophosphetes and Derivatives 737
335.7.1 Synthesis of Product Subclass 7 737
335.7.1.1 Synthesis by Ring Closure Reactions 737
335.7.1.1.1 Method 1: Ring Fused 1,2 Dihydrophosphetes by Cydoaddition of
1,2 Thiaphospholesand Ynamines 737
335.7.1.1.2 Method 2: A 1 lmino 1,2 dihydro 1 .5 phosphet 1 arnine by Cydo¬
addition of an lmino(methylene)phosphorane and
an Acetylene 738
335.7.1.1.3 Method 3: A 1 lmino 1,2 dihydro U5 phosphet 1 amine by Ring Closure
ofaPhosphabuta 1,3 dieneEffectedbyanAzide 739
335.7.1.1.4 Method 4: Phosphetium Salts of Ring Fused 1,2 Dihydrophosphetes by
Ring Closure of (Arylmethylene)chlorophosphoranes 739
XL Table of Contents
33.5.7.1.1.5 Method 5: Synthesis of a 2 Methylene 1,2 dihydrophosphete via
a Zirconium Containing Tricyclic 1,2 Dihydrophosphete 740
33.5.7.1.2 Synthesis by Ring Transformation 740
33.5.7.1.2.1 Method 1: Ring Expansion of Cycloprop 2 enylidenephosphines with
Azides 740
33.5.7.1.2.2 Method 2: 1,2 Dihydrophosphetes by Titanium Phosphorus Exchange of
a Titanacyclobutene 741
33.5.7.1.2.3 Method 3: A 1,2 Dihydrophosphete 1 Oxide by Ring Contraction of
a 2,3 Dihydro 1,2 thiaphosphole Using Ethanol 742
33.5.8 Product Subclass 8: 2,3 Dihydro 1 H phospholes and Derivatives
Cy. Keglevich and H. Szelke
33.5.8 Product Subclass 8:2,3 Dihydro 1 H phospholes and Derivatives 745
33.5.8.1 Synthesis of Product Subclass 8 745
333.8.1.1 Synthesis by Ring Closure Reactions 745
333.8.1.1.1 Method 1: 1 Alkoxy 2,3 dihydro 1 H phospholes via McCormack Cyclo
addition of Phosphorous Acid Derivatives and Buta 1,3 dienes 745
33.5.8.1.1.1.1 Variation 1: Reaction of Phosphorus Trihalides and Buta 1,3 dienes
Followed by Reaction with Alcohols 745
33.5.8.1.1.1.2 Variation 2: Reaction of a Dichlorophosphite and a Buta 1,3 diene •¦••¦• 746
33.5.8.1.1.2 Method 2: 1 Chloro 4 methyl 2,3 dihydro 1 H phospholes by Reduction
of the Phosphorus Trichloride lsoprene McCormack Cyclo
adduct 747
33.5.8.1.1.3 Method 3: 1 Phenyl 2,3 dihydro 1H phosphole 1 Oxides by McCormack
Reaction of Dichloro(phenyl)phosphine and Buta 1,3 dienes
Followed by Hydrolysis 747
333.8.1.1.4 Method 4: 1 Substituted 2,3 Dihydro 1H phosphole 1 Oxides by
Cyclization of Benzylphosphine Oxides and a,p Unsaturated
Ketones 748
33.5.8.1.1.5 Method 5: 1 Phenyl 2,3 dihydro 1 H phospholes by Intramolecular
Cyclization of But 3 enylchloro(phenyl)phosphines 749
333.8.1.2 Synthesis by Double Bond Rearrangement of 2,5 Dihydro 1H phosphole
Derivatives 749
333.8.1.2.1 Method 1: 1 Methyl 2,3 dihydro 1H phosphole 1 Oxides and Sulfides by
Acid or Base Catalyzed Isomerization 749
333.8.1.2.2 Method 2: A 5 (Diphenylphosphoryl) 2,3 dihydro 1H phosphole 1 Oxide
by Isomerization with Substitution of a 2,5 Dihydro 1H phos
pholei Oxide 750
333.8.1.2.3 Method 3: Annulated 2,3 Dihydro 1 H phospholes by Isomerization with
Substitution of 2,5 Dihydro 1 H phospholes Followed by
Ring Closure 750
333.8.1.2.4 Method 4: 3 Aryl 2,3 dihydro 1 H phosphole 1 Oxides by Isomerization
with Arylation of 2,5 Dihydro 1 H phosphole 1 Oxides 751
Table of Contents XLI
333.8.1.2.5 Method 5: 3 Bromo 1 phenyl 2,3 dihydro 1H phosphole 1 Oxide by
Isomerization with Bromination of 1 Phenyl 2,5 dihydro
1H phosphole1 Oxide 751
335.8.1.2.6 Method 6: 4 Methoxy 1 methyl 2,3 dihydro 1H phosphole 1 Oxide by
Isomerization with Chloro Substitution of 3 Chloro 1 methyl
2,5 dihydro 1H phosphole 1 Oxide 752
33.5.8.1.3 Synthesis by Elimination Reactions 752
335.8.1.3.1 Method 1: 2,3 Dihydro 1H phosphole 1 Oxides by Base Catalyzed R
earrangement of 6 Oxa 3 phosphabicyclo[3.1.0]hexanes — 752
33.5.8.1.3.2 Method 2: A 3 Substituted 2,3 Dihydro 1H phosphole 1 Oxide by
Reaction of a 6 Oxa 3 phosphabicyclo[3.1.0]hexane with
a Malonic Ester Derivative 753
335.8.1.3.3 Method 3: A 2,3 Dihydro 1H phosphole 1 Oxide by Dehydration of
a 2,3,4,5 Tetrahydro 1H phosphol 2 ol 1 Oxide 753
335.8.1.4 Synthesis by Double Bond Rearrangement of Phosphole Derivatives 754
33.5.8.1.4.1 Method 1: 3 Methylene 2,3 dihydro 1H phosphole Sulfides by
Isomerization of 3 Methyl 1H phosphole 1 Sulfides 754
335.8.1.4.2 Method 2: 3 Methylene 2,3 dihydro 1H phosphole 1 Oxides by
Thallium Ethoxide Mediated Conversion of 1 Benzyl
3 methyl 1H phospholium Salts 754
335.8.1.5 Synthesis of Fused 2,3 Dihydro 1H phospholes by Cyclopropanation of
lH Phospholes 755
335.8.1.5.1 Method 1: 2 Phosphabicyclo[3.1.0]hex 3 ene 2 Oxides by
Cyclopropanation of 1 H Phospholes with Diazomethane — 755
33.5.8.1.5.2 Method 2: A 2 Phosphabicyclo[3.1.0]hex 3 ene 2 Oxide by Intra¬
molecular Cyclopropanation of a 1 (lodomethyl)phos
pholium Salt 756
335.8.1.5.3 Method 3: 2 Phosphabicyclo[3.1.0]hex 3 ene 2 Sulfides by Cyclo¬
propanation of 1H Phosphole 1 Sulfides with Ethyl
Diazoacetate 756
335.9 Product Subclass 9:1,2,3,4 Tetrahydrophosphinines and Derivatives
Gy. Keglevich and H. Szelke
33.5.9 Product Subclass 9:1,2,3,4 Tetrahydrophosphinines and Derivatives • • ¦ • 759
335.9.1 Synthesis of Product Subclass 9 759
335.9.1.1 Synthesis by Ring Closure Reactions 759
335.9.1.1.1 Method 1: 1,2,3,4 Tetrahydrophosphinines by Cycloaddition of an
In Situ Formed Phosphabuta 1,3 diene and Unsaturated
Esters 759
335.9.1.1.2 Method 2: A 1,2,3,4 Tetrahydrophosphinine 1 Oxide by Cyclization of
a Diallylphosphine Oxide with Isomerization 759
335.9.1.2 Synthesis by Double Bond Rearrangement of Tetrahydrophosphinines 760
335.9.1.2.1 Method 1: 1,2,3,4 Tetrahydrophosphinines via Bromination of
the Corresponding 1,2,3,6 Tetrahydrophosphinines 760
XUI Table of Contents _„
33.5.9.1.3 Synthesis by Selective Saturation 761
333.9.1.3.1 Method 1: A 1,2,3,4 Tetrahydrophosphinine 1 Oxide by Hydrogenation
of a 1,2 Dihydrophosphinine 1 Oxide 761
333.9.1.3.2 Method 2: A4 (Dichloromethylene) 1,2,3,4 tetrahydrophosphinine
1 Oxide via Hydroboration of the Corresponding 1,4 Dihydro
phosphinine 1 Oxide 761
33.5.9.1.3.3 Method 3: A 1,2,3,4 Tetrahydrophosphinin 4 one 1 Oxide by Hydrolysis
of a X5 Phosphinine 761
33.5.10 Product Subclass 10:1,4 Dihydrophosphinines and Derivatives
Cy. Keglevich and H. Szelke
33.S.10 Product Subclass 10:1,4 Dihydrophosphinines and Derivatives 765
33.5.10.1 Synthesis of Product Subclass 10 765
33.5.10.1.1 Synthesis by Ring Closure Reactions 765
33.5.10.1.1.1 Method 1: 1,4 Dihydrophosphinines by Reaction of 1,4 Diynes with
Arylphosphines 765
335.10.1.1.2 Method 2: 1,4 Dihydrophosphinines by Reaction of Dilithiated
Penta 1,4 dienes with Dichlorophosphines 766
33.5.10.1.2 Synthesis by Ring Transformation 766
33.5.10.1.2.1 Method 1: A Biphosphinin 4(1H) ylidene 1,1' Dioxide by Photolysis of
a 2 Phosphabicyclo[3.1 .Ojhexane Oxide 766
335.10.1.3 Synthesis from X5 Phosphinines and X3 Phosphinines 767
33.5.10.1.3.1 Method 1: 1,4 Dihydrophosphinine 1 Oxides by Isomerization of
X5 Phosphinines 767
33.5.10.1.3.2 Method 2: A 1,4 Dihydrophosphinine 1 Oxide via the Chlorination of
a X3 Phosphinine 767
33.5.10.1.3.3 Method 3: A4 Methylene 1,4 dihydrophosphinine 1 Oxide by
a Lewis Acid Catalyzed Rearrangement of a 4 Methyl
X5 phosphinine 768
335.10.1.3.4 Method 4: 4 Methylene 1,4 dihydrophosphinine 1 Oxides via
Enolization of a X5 Phosphinine 4 carbaldehyde 768
33.5.10.1.3.5 Method 5: A 1',4' Dihydro 2,4' biphosphinine by Special Reaction of
a X3 Phosphinine in the Presence of Lithium 2,2,6,6 Tetra
methylpiperidide 769
335.10.1.4 Synthesis by Substituent Modification 770
335.10.1.4.1 Method 1: A Biphosphinin 4(1H) ylidene 1,1' Dioxide by Coupling of
Two Units of a Phosphinin 4(1H) one 1 Oxide 770
Keyword Index 773
Author Index 817
Abbreviations 861 |
| adam_txt |
XIII
Table of Contents
Introduction
G. A. Molander
Introduction 1
33.1 Product Class 1: Alk 1 enyl Sulfur Compounds
33.1.1 Product Subclass 1: Alk 1 enesulfonic Acids and Derivatives
J. C. Carretero and R. C. Arrayas
33.1.1 Product Subclass 1: Alk 1 enesulfonic Acids and Derivatives 13
33.1.1.1 Synthesis of Product Subclass 1 13
33.1.1.1.1 Method 1: Synthesis from 2 Chloroalkanesulfonic Acid Derivatives 13
33.1.1.1.2 Method 2: Condensations of the Carbanions of Sulfonic Acid Derivatives
with Carbonyl Compounds 14
33.1.1.1.2.1 Variation 1: Aldol Type Condensations and Related Processes 14
33.1.1.1.2.2 Variation 2: Wadsworth Emmons Alkenation Reactions 15
33.1.1.1.3 Method 3: Cyclic Alk 1 enesulfonic Esters and Sulfonamides by
Metathesis Reactions 16
33.1.1.1.4 Methods 4: Miscellaneous Syntheses of Alk 1 enesulfonic Acid Derivatives
from Other Sulfur Compounds 17
33.1.2 Product Subclass 2: Alk 1 enyl Sulfones
J. C. Carretero and R. C. Arrayas
33.1.2 Product Subclass 2: Alk 1 enyl Sulfones 19
33.1.2.1 Synthesis of Product Subclass 2 19
33.1.2.1.1 Method 1: Sulfonylation of Nucleophilic Alkenyl Reagents 19
33.1.2.1.2 Method 2: Condensation of Sulfonyl Carbanions with
Carbonyl Compounds 20
33.1.2.1.2.1 Variation 1: Aldol Type Condensation and Dehydration 20
33.1.2.1.2.2 Variation 2: Knoevenagel Condensation of Activated Sulfones 22
33.1.2.1.2.3 Variation 3: Condensation of Sulfinyl(sulfonyl)methanes with Aldehydes 23
33.1.2.1.2.4 Variation 4: Horner Wadsworth Emmons Alkenation of
a Sulfonyl Phosphonates 24
33.1.2.1.2.5 Variation 5: Peterson Alkenation of a Silylalkyl Sulfones 26
33.1.2.1.3 Method 3: Sulfonylation of Alkenes Followed by Elimination 28
33.1.2.1.3.1 Variation 1: Chlorosulfenylation of Alkenes, Followed by Sulfur Oxidation
and Elimination 28
33.1.2.1.3.2 Variation 2: Sulfonomercuration of Alkenes Followed by Demercuration 29
33.1.2.1.3.3 Variation 3: Selenosulfonylation of Alkenes Followed by
Selenium Oxidation 30
XIV Table of Contents
33.1.2.1.3.4 Variation 4: lodosulfonylation of Alkenes Followed by Dehydroiodination 31
33.1.2.1.4 Method 4: Sulfonylation of Alkynes 33
33.1.2.1.5 Method 5: Functionalization of Alk 1 ynyl Sulfones 34
33.1.2.1.5.1 Variation 1: Addition Reactions 35
33.1.2.1.5.2 Variation 2: Cycloaddition Reactions 37
33.1.2.1.6 Method 6: Oxidation of Alk 1 enyl Sulfides and Sulfoxides 37
33.1.2.1.7 Method 7: Functionalization of Allyl Sulfones and Derivatives 38
33.1.2.1.8 Method 8: Functionalization of Simple Alk 1 enyl Sulfones 40
33.1.2.1.8.1 Variation 1: a Functionalization 40
33.1.2.1.8.2 Variation 2: Heck Reaction 42
33.1.2.1.8.3 Variation 3: Cross Metathesis Reactions 43
33.1.2.1.8.4 Variation 4: Diels Alder Reactions of Dienyl Sulfones 44
33.1.2.1.8.5 Variation 5: Substitution of P Functionalized Alk 1 enyl Sulfones 45
33.1.3 Product Subclass 3: S Alk 1 enylsulfoximides
J. C. Carretero and R. G. Arrayas
33.1.3 Product Subclass 3: S Alk 1 enylsulfoximides 51
33.1.3.1 Synthesis of Product Subclass 3 51
33.1.3.1.1 Method 1: Condensation of Sulfonimidoyl Carbanions with
Carbonyl Compounds 51
33.1.3.1.1.1 Variation 1: Aldol Type Condensations of a Sulfonimidoyl Carbanions and
the Dehydration of the Intermediate P Hydroxylated Sulfox
imides 52
33.1.3.1.1.2 Variation 2: Peterson and Wadsworth Emmons Alkenation Reactions • • • • 54
33.1.3.1.2 Method 2: Imination of Alk 1 enyl Sulfoxides 55
33.1.3.1.3 Method 3: Functionalization of Simple S Alk 1 enyl and
S Alk 2 enylsulfoximides 56
33.1.4 Product Subclass 4: Alk 1 enesurfinic Acids and Derivatives
J. C. Carretero and R. G. Arrayas
33.1.4 Product Subclass 4: Alk 1 enesurfinic Acids and Derivatives 59
33.1.4.1 Synthesis of Product Subclass 4 59
33.1.4.1.1 Method 1: Reaction of Allenes and Alkynes with Sulfur Dioxide 59
33.1.4.1.2 Method 2: Oxidative Fragmentation of Alk 1 enyl Benzyl Sulfoxides 60
33.1.4.1.3 Method 3: S Oxidation of lsothiazol 3(2H) ones 61
33.1.5 Product Subclass 5: Alk 1 enyl Sulfoxides, Sulfimides,
and Related Compounds
J. C. Carretero and R. G. Arrayas
33.1.5 Product Subclass 5: Alk 1 enyl Sulfoxides, Sulfimides,
and Related Compounds 65
33.1.5.1 Synthesis of Product Subclass 5 66
Table of Contents XV
33.1.5.1.1 Method 1: Sulfinylation of Nucleophilic Alkenyl Reagents 66
33.1.5.1.1.1 Variation 1: Sulfinylation with Menthyl 4 Toluenesulfinate 66
33.1.5.1.1.2 Variation 2: Sulfinylation with Other Enantiopure Sulfinylating Reagents 67
33.1.5.1.2 Method 2: Condensations of Sulfinyl Carbanions (and Related Species)
with Carbonyl Compounds 69
33.1.5.1.2.1 Variation!: Aldol Type Condensations and Dehydrations 69
33.1.5.1.2.2 Variation 2: Mannich Type Reactions 72
33.1.5.1.2.3 Variation 3: Knoevenagel Type Condensations 73
33.1.5.1.2.4 Variation 4: Wadsworth Emmons Alkenation 75
33.1.5.1.2.5 Variation 5: Wittig and Horner Wittig Reactions 79
33.1.5.1.2.6 Variation 6: Peterson Alkenation 80
33.1.5.1.3 Method 3: Conversions of Alkynes into Alkenyl and Allenyl Sulfoxides ••• 81
33.1.5.1.3.1 Variation 1: Additions of Sulfenic Acids to Alkynes 82
33.1.5.1.3.2 Variation 2: Reactions of Sulfenyl Chlorides with Propargylic Alcohols — 83
33.1.5.1.4 Method 4: Addition Reactions to Alkynyl Sulfoxides 84
33.1.5.1.5 Method 5: Oxidation of Alkenyl Sulfides 86
33.1.5.1.6 Method 6: Functionalization of Alkenyl Sulfoxides and Derivatives 88
33.1.5.1.6.1 Variation 1: a Functionalization 88
33.1.5.1.6.2 Variation 2: The Heck Reaction 90
33.1.5.1.6.3 Variation 3: The Stille and Other Palladium Catalyzed
Cross Coupling Reactions 92
33.1.5.1.6.4 Variation 4: Synthesis from Other Alkenyl Sulfoxides 93
33.1.6 Product Subclass 6: Alk 1 enethiols
J. Drabowicz, P. Kietbasinski, and M. Mikotajczyk
33.1.6 Product Subclass 6: Alk 1 enethiols 101
33.1.6.1 Synthesis of Product Subclass 6 101
33.1.6.1.1 Methodi: Reaction of Alkenes with Elemental Sulfur 101
33.1.6.1.2 Method 2: C S Bond Cleavage of Alkenyl Sulfides 101
33.1.6.1.3 Method 3: Reaction of f Alkenyl(phenyl) X3 iodanes with Thioamides 102
33.1.6.1.4 Method 4: Reaction of Haloalkenes with Hydrogen Sulfide 102
33.1.6.1.5 Method 5: Retro Diels Alder Reactions of 9,10 Ethano
9,10 dihydroanthracene 11 thiols 103
33.1.6.1.6 Method 6: Pyrolysis of 1,2 EthanedithiolorThiirane 103
33.1.6.1.7 Method 7: Addition of Hydrogen Sulfide to Alkynes 103
33.1.6.1.8 Method 8: Enethiolization of Thiocarbonyl Compounds 104
33.1.7 Product Subclass 7: Metal Alk 1 enethiolates
J. Drabowicz, P. Kietbasinski, and M. MikoJajczyk
33.1.7 Product Subclass 7: Metal Alk 1 enethiolates 109
33.1.7.1 Synthesis of Product Subclass 7 109
33.1.7.1.1 Methodi: Alkali Metal Cleavage of Alk 1 enyl Alkyl Sulfides 109
33.1.7.1.2 Method 2: Hydrolysis of Alk 1 enyl Thiolacetates 109
XVI Table of Contents
33.1.7.1.3 Method 3: Transformations of Thiiranes and Thiirane 5 Oxides 110
33.1.7.1.4 Method4: Deprotonation of Thiocarbonyl Compounds Ill
33.1.8 Product Subclass 8: Alk 1 enyl Sulfides
J. Drabowicz, P. Kietbasiriski, and M. Mikotajczyk
33.1.8 Product Subclass 8: Alk 1 enyl Sulfides 113
33.1.8.1 Synthesis of Product Subclass 8 113
33.1.8.1.1 Synthesis of Acyclic Alk 1 enyl Sulfides 113
33.1.8.1.1.1 Method 1: Alkylation of Alk 1 enethiolates 113
33.1.8.1.1.2 Method 2: Transformations of 1 Haloalkenes and Their Analogues 114
33.1.8.1.1.2.1 Variation 1: Nucleophilic Substitution by Thiolate Anions and
Their Analogues 114
33.1.8.1.1.2.2 Variation 2: Reactions of 1 Bromoalkenes with Trialkylstannyl Sulfides ••• 115
33.1.8.1.1.2.3 Variation 3: Reactions with Copper Thiolates 116
33.1.8.1.1.2.4 Variation 4: Palladium Catalyzed Reactions with Thiolanes and
Their Equivalents 116
33.1.8.1.1.2.5 Variation 5: Photochemical Reactions between 1 Bromoalk 1 enes and
Sulfides 119
33.1.8.1.1.2.6 Variation 6: Using Alk 1 enylmercury(ll) Halides 119
33.1.8.1.1.2.7 Variation?: Using Alk 1 enyltributylstannanes 120
33.1.8.1.1.2.8 Variation 8: Using (Trimethylsiloxy)alkenes •• 121
33.1.8.1.1.3 Method 3: Syntheses from Alkyl Sulfides 121
33.1.8.1.1.3.1 Variation 1: Dehydrohalogenation of Haloalkyl Sulfides 121
33.1.8.1.1.3.2 Variation 2: Manganese(IV) Oxide Promoted Reactions of Sulfides with
Acetyl Chloride 125
33.1.8.1.1.3.3 Variation 3: Peterson Reactions of a Silyl Derivatives 125
33.1.8.1.1.3.4 Variation 4: Decarboxylation of 2 (Methylsulfanyl)propanoic Acid 127
33.1.8.1.1.4 Method 4: Syntheses from Dithioacetals and Trithioorthoformates 128
33.1.8.1.1.4.1 Variation 1: Reactions with Sulfenyl Chlorides 128
33.1.8.1.1.4.2 Variation 2: Copper or Lewis Acid Mediated Cleavages of Sulfides 129
33.1.8.1.1.4.3 Variation 3: Stereoselective Reduction of Ketene Dithioacetals 129
33.1.8.1.1.4.4 Variation 4: Phosphite Mediated Elimination Reactions 130
33.1.8.1.1.4.5 Variation 5: From Trithioorthoformates 130
33.1.8.1.1.5 Method 5: Aldol Condensations of Sulfides Bearing an
Electron Withdrawing a Substituent 131
33.1.8.1.1.6 Method 6: Syntheses via Organophosphorus Reagents 131
33.1.8.1.1.6.1 Variation 1: From Phosphorus Ylides 131
33.1.8.1.1.6.2 Variation 2: Wadsworth Emmons Horner Reactions 132
33.1.8.1.1.7 Method 7: Synthesis from Alkyl Sulfoxides 134
33.1.8.1.1.7.1 Variation 1: Pummerer Type Rearrangement of ct Chloroalkyl Sulfoxides 134
33.1.8.1.1.7.2 Variation 2: lodotrimethylsilane lnduced Elimination Deoxygenation of
Sulfoxides 135
33.1.8.1.1.8 Method 8: Deoxygenation of Alk 1 enyl Sulfoxides 135
33.1.8.1.1.9 Method 9: Synthesis from Alkynyl Sulfides 136
33.1.8.1.1.9.1 Variation 1: Reduction of Alkynyl Sulfides 136
Table of Contents XVII
33.1.8.1.1.9.2 Variation 2: Hydroboration of Alkynyl Sulfides 137
33.1.8.1.1.9.3 Variation 3: Tantalum Mediated Additions to Alkynyl Sulfides 137
33.1.8.1.1.9.4 Variation 4: Stereoselective Addition of Grignard Reagents to
Alkynyl Sulfides 138
33.1.8.1.1.9.5 Variation 5: Addition of Organocopper Reagents to Alkynyl Sulfides 138
33.1.8.1.1.10 Method 10: Addition of Thiols or Their Derivatives to Alkynes 139
33.1.8.1.1.10.1 Variation 1: Free Radical Additions 139
33.1.8.1.1.10.2 Variation 2: Addition of Thiolates to Alkynes 141
33.1.8.1.1.10.3 Variation 3: Metal Catalyzed Addition of Thiols and Their
Borabicyclo Derivatives to Alkynes 143
33.1.8.1.1.10.4 Variation 4: Addition of Sulfenyl Halides or Sulfenamides to Alkynes 147
33.1.8.1.1.11 Method 11: Ring Opening of Epoxy Sulfides 149
33.1.8.1.1.12 Method 12: Reaction of Benzyne with Thiiranes 151
33.1.8.1.1.13 Method 13: Reaction of N Tosylsulfimides with Potassium tert Butoxide 151
33.1.8.1.2 Synthesis of Cyclic Alk 1 enyl Sulfides 151
33.1.8.1.2.1 Method 1: Reaction of Chlorotropylium Salts with Thiols 152
33.1.8.1.2.2 Method 2: Alkylation of Cycloalk 1 ene 1 thiolates 152
33.1.8.1.2.3 Method 3: Dehydrochlorination of Cyclic Sulfides 152
33.1.8.1.2.3.1 Variation 1: Chlorosulfenylation Dehydrochlorination of Cycloalkenes ¦¦• 152
33.1.8.1.2.3.2 Variation 2: Addition of Thiols to Cycloalk 2 enones, Followed by
Chlorination Dehydrochlorination of the Adducts 153
33.1.8.1.2.4 Method 4: Synthesis from Cycloalkanones and Dithioacetals or Thiols 154
33.1.8.1.2.5 Method 5: Pummerer Reaction of Cyclic Sulfoxides 155
33.1.8.1.2.6 Method 6: Intramolecular Cyclization of Sulfines Derived from
S Unsaturated Dithioesters 156
33.1.8.1.2.7 Method 7: Intramolecular Trapping Reactions of Enethiols
Functionalized by a Silyl Croup 157
33.1.8.1.3 Synthesis of Polyenyl Sulfides 157
33.1.8.1.3.1 Method 1: Sulfanylbuta 1,3 dienes via Elimination Reactions 157
33.1.8.1.3.1.1 Variation 1: Elimination of a Thiol from Bis(dithioacetals) 157
33.1.8.1.3.1.2 Variation 2: Removal of Methanol from Aryl 4,4 Dimethoxybut 2 enyl
Sulfides 158
33.1.8.1.3.1.3 Variation 3: Extrusion of Sulfur Dioxide from 3 Sulfanyl 2,5 dihydro
thiophene 1,1 Dioxides 160
33.1.8.1.3.1.4 Variation 4: Flash Vacuum Pyrolysis of Sulfur Containing Cyclic Derivatives 160
33.1.8.1.3.1.5 Variation 5: Elimination Reactions of Aryl 2 Chlorobut 3 enyl Sulfides ••• 161
33.1.8.1.3.1.6 Variation 6: Elimination Reactions of 2 Methyl 4 sulfanylbut 3 en 2 ols 161
33.1.8.1.3.2 Method 2: Addition of Thiols to But 1 en 3 ynes 162
33.1.8.1.3.3 Method3: Reduction of (1£) But 1 en 3 ynyl Ethyl Sulfides 163
33.1.8.1.3.4 Method 4: Base Catalyzed Ring Opening Reactions of
Sulfur Containing Heterocycles 163
33.1.8.1.3.5 Method 5: Horner Wittig Reaction of Alkenyl Phosphine Oxides
Functionalized with a Phenylsulfanyl Substituent 165
XVIII Table of Contents „„.
33.1.9 Product Subclass 9: Alk 1 enylsulfonium Salts
J. Drabowicz, P. Kietbasiriski, and M. Mikotajczyk
33.1.9 Product Subclass 9: Alk 1 enylsulfonium Salts 169
33.1.9.1 Synthesis of Product Subclass 9 169
33.1.9.1.1 Method 1: Dehydrohalogenation of (2 Haloalkyl)sulfonium Salts 169
33.1.9.1.2 Method 2: S Alkylation of Alk 1 enyl Sulfides 172
33.1.9.1.3 Method 3: Synthesis from Dithioacetals 173
33.1.9.1.4 Method 4: Synthesis from Alkenes 173
33.1.9.1.5 Method 5: Synthesis from Sulfonium Ylides Stabilized by
a Phosphoryl Substituent 174
33.1.10 Product Subclass 10: Alk 1 enesulfenic Acid Derivatives
J. Drabowicz, P. Kietbasinski, and M. Mikotajczyk
33.1.10 Product Subclass 10: Alk 1 enesulfenic Acid Derivatives 177
33.1.10.1 Synthesis of Product Subclass 10 177
33.1.10.1.1 Method 1: Alk 1 enesulfenyl Chlorides by Chlorination of Enethiols or
Alk 1 enyl Sulfides 177
33.1.10.1.2 Method 2: Alk 1 enesulfenyl Chlorides from Allenes and Sulfur Dichloride 178
33.1.10.1.3 Method 3: Alk 1 enesulfenyl Chlorides from Alkynes and
Sulfur Dichloride 178
33.1.10.1.4 Method 4: Alkenesulfenamides by Addition of Amidosulfenyl Chlorides
to Alkynes 179
33.1.10.1.5 Methods: Alk 1 enesulfenamides from Alk 1 enesulfenate Anions 180
33.1.10.1.6 Method 6: Alk 1 enesulfenic Acids by the Enethiolization of Sulfines •••• 181
33.1.11 Product Subclass 11: Alk 1 enyl Disulfides
J. Drabowicz, P. Kiefbasiriski, and M. Mikolajczyk
33.1.11 Product Subclass 11: Alk 1 enyl Disulfides 183
33.1.11.1 Synthesis of Product Subclass 11 183
33.1.11.1.1 Method 1: Sulfenylation of Alkenethiolate Anions 183
33.1.11.1.2 Method 2: Addition of Nucleophiles to Sulfines 185
33.1.12 Product Subclass 12: Thietes and Derivatives
E. Block
33.1.12 Product Subclass 12: Thietes and Derivatives 187
33.1.12.1 Synthesis of Product Subclass 12 188
33.1.12.1.1 Synthesis by Ring Closure Reactions 188
33.1.12.1.1.1 Method 1: Reaction of Sulfenes and Ynamines or Ketene O,N Acetals •¦• 188
33.1.12.1.1.2 Method 2: Photocycloaddition of Thiones to Alkynes 189
33.1.12.1.1.3 Method 3: Reaction of a Perfluorinated Alkeneand tert Butanethiol — 190
Table of Contents XIX
33.1.12.1.1.4 Method 4: Electrocyclic Ring Closure of Enethiones 191
33.1.12.1.2 Synthesis by Ring Transformation 191
33.1.12.1.2.1 Method 1: Ring Enlargement of Diazothiiranimines 191
33.1.12.1.2.2 Method 2: Ring Enlargement of Thiirenes 192
33.1.12.1.2.2.1 Variation 1: Reaction of a Sulfonium Ylide with Diphenylthiirene Dioxide 192
33.1.12.1.2.2.2 Variation 2: From an S Methylthiirenium Ion 192
33.1.12.1.2.3 Method 3: Ring Contraction of Thiophene 1,1 Dioxides 192
33.1.12.1.2.4 Method 4: Synthesis from Thiophenones 193
33.1.12.1.3 Elimination Reactions from Thietanes 194
33.1.12.1.3.1 Method 1: Cope and Hofmann Eliminations 194
33.1.12.1.3.2 Method 2: Elimination of a Hydrogen Halide or Ethanol 195
33.M2.1.4 Synthesis by Substituent Modification 197
33.1.12.1.4.1 Substitution of Hydrogen 197
33.1.12.1.4.1.1 Method 1: Addition and Elimination of Halogen 197
33.1.12.1.4.2 Substitution of Halogens 197
33.1.12.1.4.2.1 Method 1: Michael Addition 197
33.1.12.1.4.3 Modification of Substituents 197
33.1.12.1.4.3.1 Method 1: Enolization/Acylation of Thietan 3 one Derivatives 197
33.1.12.1.4.3.2 Method 2: Double Bond Isomerization 198
33.1.12.1.4.3.3 Method 3: Hydrogenation of 2 Methylenethietes 198
33.1.12.1.4.3.4 Method 4: [4+2] and [2 + 2] Cycloadditions of 2 Methylenethietes 198
33.1.12.1.5 Addition Reactions 199
33.1.12.1.5.1 Method 1: S Alkylation Using Methyl Trifluoromethanesulfonate 199
33.1.12.1.5.2 Method 2: S Oxidation Using Monoperoxyphthalic Acid 199
33.1.12.2 Applications of Product Subclass 12 in Organic Synthesis 200
33.1.12.2.1 Method 1: Ring Opening to Propenethial S,5 Dioxides and
Subsequent Cycloaddition or Rearrangement 200
33.1.13 Product Subclass 13: 2,3 Dihydrothiophenes and Derivatives
E. Block
33.1.13 Product Subclass 13: 2,3 Dihydrothiophenes and Derivatives 203
33.1.13.1 Synthesis of Product Subclass 13 204
33.1.13.1.1 Synthesis by Ring Closure Reactions 204
33.1.13.1.1.1 Methodi: Reaction of Zirconacycles with Sulfur Monochloride 204
33.1.13.1.1.2 Method 2: Reaction of 1 (1 Adamantylcarbonylmethyl)pyridinium
Bromide with (Arylmethylene)cyanothioacetamides 204
33.1.13.1.1.3 Method 3: 1,3 Dipolar Cycloaddition of Mesoionic Thiazolium 4 olates
to Nitroalkenes 205
33.1.13.1.1.4 Method 4: Heating Dialk 1 enyl Disulfides 205
33.1.13.1.1.5 Method 5: Enethiolization of co Halothioacylsilanes 206
33.1.13.1.1.6 Method 6: Synthesis from But 3 ynethiols and Derivatives 206
XX Table of Contents
33.1.13.1.1.6.1 Variation 1: Using Base or Hexacarbonylchromium Catalysis 206
33.1.13.1.1.6.2 Variation 2: From Halocyclizations 207
33.1.13.1.1.7 Method 7: Synthesis from 4,4 Dihalobut 3 enethiols 208
33.1.13.1.1.7.1 Variation 1: From 3 (Difluoromethylene) 2 methyl 6 phenylhexane
1 thiol 208
33.1.13.1.1.7.2 Variation 2: From 4,4 Dibromo 3 methylbut 3 ene 1 thiol 208
33.1.13.1.1.8 Method 8: Synthesis from 5 Substituted Pentan 2 ones 208
33.1.13.1.1.8.1 Variation 1: From 5 Sulfanylated Pentan 2 ones or
5 Bromopentan 2 ones 208
33.1.13.1.1.8.2 Variation 2: From O Ethyl S (4 Oxobutyl) Dithiocarbonates 209
33.1.13.1.1.9 Method 9: Intramolecular Michael Additions 210
33.1.13.1.1.10 Method 10: Cyclization of a Phosphonovinyl Radicals 210
33.1.13.1.1.11 Method 11: Base Induced Cyclizations of Alkynyl Benzyl Sulfides 211
33.1.13.1.1.12 Method 12: Intramolecular Wittig Reactions of Thioesters 212
33.1.13.1.1.13 Method 13: Intramolecular Titanocene(ll) Promoted Alkenations of
Thioesters 212
33.1.13.1.1.14 Method 14: Photocyclization of Bis(2 phenylvinyl) Sulfide 213
33.1.13.1.2 Synthesis by Ring Transformation 214
33.1.13.1.2.1 Method 1: Formal Exchange of Ring Members with Retention of Ring Size 214
33.1.13.1.2.2 Method 2: Light Induced Ring Contraction of 1,2 Dithiins 214
33.1.13.1.2.3 Method 3: Electrocyclic Ring Closure of Thionins 215
33.1.13.1.3 Synthesis by the Elimination Reactions of Thiolanes 215
33.1.13.1.3.1 Method 1: Synthesis from 2 Acetoxy and
2 (Benzoyloxy)tetrahydrothiophenes 215
33.1.13.1.3.2 Method 2: Synthesis from 2 or 3 Hydroxy , 3 Bromo ,
or2 (Alkylsulfanyl)tetrahydrothiophenes 216
33.1.13.1.3.3 Method 3: Bamford Stevens Elimination of the Tosylhydrazone of
Dihydrothiophen 3(2H) one 217
33.1.13.1.4 Synthesis by Substituent Modification 218
33.1.13.1.4.1 Substitution of Hydrogen or Metals 218
33.1.13.1.4.1.1 Method 1: Lithiation of 2.3 Dihydrothiophene and Its Reactions with
Electrophiles 218
33.1.13.1.4.1.2 Method 2: Replacement of Tin by Hydroxyalkyl Croups 218
33.1.13.1.4.2 Substitution of Heteroatoms 219
33.1.13.1.4.2.1 Method 1: Nucleophilic Substitutions of 3 Bromo 2,3 dihydrothiophene
1,1 Dioxide 219
33.1.13.1.4.2.2 Method 2: Substitution of a Trifluoromethylsulfonyloxy Group by a Metal 220
33.1.13.1.4.3 Addition Reactions 221
33.1.13.1.4.3.1 Method 1: Reduction of Thiophenes 221
33.1.13.1.4.3.1.1 Variation 1: Birch Reduction 221
33.1.13.1.4.3.1.2 Variation 2: Samarium(ll) Iodide Mediated Double Electrophilic Reduction 221
33.1.13.1.4.3.2 Method 2: Dimerization of 2,3 Dihydrothiophene and Its 1,1 Dioxide ••• 222
33.1.13.1.4.3.3 Method 3: Addition Reactions Involving Thiophene 1 Oxides 223
33.1.13.1.4.3.3.1 Variation 1: Dihydrodiol Formation or Oxidation/Dimerization 223
33.1.13.1.4.3.4 Method 4: Nucleophilic Additions to Thiophene 1 Oxides or 1,1 Dioxides 224
Table of Contents XXI
33.1.13.1.4.3.5 Method 5: Electrophilic Additions toThiophene 1,1 Dioxides 225
33.1.13.1.4.3.6 Method 6: Diels Alder Additions 226
33.1.13.1.4.3.7 Method 7: Ylide Formation 226
33.1.13.1.4.3.8 Method 8: Oxidation of the Sulfur Atom 227
33.1.13.1.4.3.9 Method 9: Sulfilimine Formation 227
33.1.13.1.4.4 Modification of Substituents 228
33.1.13.1.4.4.1 Method 1: Reduction of the Sulfoxide Group 228
33.1.13.1.4.4.2 Method 2: 4,5 Dihydro 2 thienyl 2 Trifluoromethanesulfonate by
Enolization of Thiophen 2(3H) one 228
33.1.13.1.4.4.3 Method 3: Isomerization of 2,5 Dihydrothiophenes 228
33.1.13.1.4.4.4 Method 4: Base Catalyzed Isomerization of 2,5 Dihydrothiophene
1,1 Dioxides 229
33.1.13.2 Applications of Product Subclass 13 in Organic Synthesis 229
33.1.13.2.1 Method 1: Use as a Protecting Croup for Alcohols 229
33.1.13.2.2 Method 2: Nickel Catalyzed Replacement of a Vinylic C S Bond with
a C C Bond 230
33.1.13.2.3 Method 3: Aromatization of 2,3 Dihydrothiophenes 230
33.1.13.2.4 Method 4: Photoisomerism of 2,3 Dihydrothiophenes to
2 Alkylidenetetrahydrothiophenes 230
33.1.13.2.5 Method 5: Conversion of 2,3 Dihydrothiophenes into
6 Oxo 2 thiabicyclo[3.2.0]heptane 4 carboxylic Acids 230
33.1.13.2.6 Method 6: [2+2] Photochemical Cycloadditions to
2,3 Dihydrothiophene 1,1 Dioxide 231
33.1.13.2.7 Method 7: 3,4 Dihydro 2H thiopyrans from 2,3 Dihydrothiophenium
Methylides 232
33.1.14 Product Subclass 14:3,4 Dihydro 2H thiopyrans and Derivatives
E. Block
33.1.14 Product Subclass 14:3,4 Dihydro 2H thiopyrans and Derivatives 235
33.1.14.1 Synthesis of Product Subclass 14 235
33.1.14.1.1 Synthesis by Ring Closure Reactions 235
33.1.14.1.1.1 Method 1: Synthesis from 1,5 Diketones and Hydrogen Sulfide/
Hydrogen Chloride, Phosphorus Pentasulfide,
or Hexamethyldisilathiane 236
33.1.14.1.1.2 Method 2: Synthesis from 1,4 Dien 3 ones and 1 En 4 yn 3 ones by
Michael Addition 237
33.1.14.1.1.3 Method 3: Synthesis from Propenethial 238
33.1.14.1.1.4 Method 4: Synthesis from Propenethial S,S Dioxide 239
33.1.14.1.1.5 Method 5: Synthesis from Other Enethiones 239
33.1.14.1.1.6 Method 6: Synthesis from Benzothietes 242
33.1.14.1.1.7 Method 7: Double Michael Additions of Malonate Anions to
Alk 1 enylAlk 1 ynylSulfones 242
33.1.14.1.1.8 Method 8: Combination of Enones and Two Three Atom Fragments — 243
33.1.14.1.1.9 Method 9: Photolysis of Pent 4 ynethiol 243
XXII Table of Contents
33.1.14.1.1.10 Method 10: Synthesis from (o Halothioacylsilanes 243
33.1.14.1.1.11 Method 11: Synthesis from 3 Methyl 6 sulfanylhexan 2 ones 244
33.1.14.1.1.12 Method 12: Synthesis from a 5,5 Dibromopent 4 enethiol or
a 5,5 Dibromopent 4 enyl Sulfide 244
33.1.14.1.1.13 Method 13: Synthesis from 1 (Arenesulfonyl) 5 iodobut 1 enyl
Methyl Sulfides 244
33.1.14.1.1.14 Method 14: Thermal Rearrangement of Prop 2 ynyl Vinyl Sulfide 245
33.1.14.1.1.15 Method 15: Cope Rearrangement of Thiocarbonyl Compounds 245
33.1.14.1.1.16 Method 16: Electrocyclic Ring Closure of (3£,5Z) 1,1,1,7,7,7 Hexafluoro
3,4,5 tris(trifluoromethyl)hepta 3,5 diene 2 thione 246
33.1.14.1.1.17 Method 17: Cyclization of S Allyl a Phosphonovinyl Radicals 246
33.1.14.1.2 Synthesis by Ring Transformation 247
33.1.14.1.2.1 Method 1: Ring Enlargement of Acyldihydrothiophenes 247
33.1.14.1.2.2 Method 2: Ring Enlargement of 4,5 Dihydrothiophenium and
Thiophenium 1 Methylides 248
33.1.14.1.3 Synthesis from Dihydro and Tetrahydrothiopyrans 248
33.1.14.1.3.1 Method 1: Rearrangement and/or Elimination Reactions 248
33.1.14.1.4 Synthesis by Substituent Modification 250
33.1.14.1.4.1 Substitution of Hydrogen 250
33.1.14.1.4.1.1 Method 1: Lithiation of 3,4 Dihydro 2H thiopyrans, 2H Thiopyrans,
and 4H Thiopyrans 250
33.1.14.1.4.2 Substitution of Metals 250
33.1.14.1.4.2.1 Method 1: Replacement of Lithium by Organostannyl and
Organosilyl Groups 250
33.1.14.1.4.3 Addition Reactions 250
33.1.14.1.4.3.1 Method 1: Dimerization of 3,4 Dihydro 2H thiopyran 250
33.1.14.1.4.3.2 Method 2: Oxidation of the Sulfur Atom 251
33.1.14.1.4.3.3 Method 3: Sulfilimine Formation 251
33.1.14.1.4.4 Modification of Substituents 251
33.1.14.1.4.4.1 Method 1: Enolization of Dihydrothiopyranones 251
33.1.14.1.4.4.2 Method 2: Cationic Interconversion of 4H Thiopyrans into 2H Thiopyrans 252
33.1.14.1.4.4.3 Method 3: Base Induced Conversions of 2H Thiopyrans into
4H Thiopyrans 252
33.1.14.1.4.4.4 Method 4: Photochemical Conversion of a 2H Thiopyran into
a 4H Thiopyran 254
33.1.14.2 Applications of Product Subclass 14 in Organic Synthesis 254
33.1.14.2.1 Method 1: Nickel Catalyzed Replacement of a Vinylic C—S Bond with
a C C Bond 254
33.1.14.2.2 Method 2: Synthesis of Thiopyrylium Salts 255
33.1.14.2.3 Method 3: Synthesis of 4 Methylene 2,6 diphenyl 4H thiopyrans 255
33.1.14.2.4 Method 4: Synthesis of Chiral Auxiliaries for
Corey Chaykovsky Epoxidation 255
33.1.14.2.5 Method 5: Protecting Croup for Alcohols 256
Table of Contents XXIII
33.1.1s Product Subclass 15: 2,3,4,5 Tetrahydrothiepins, Larger Rings,
and Derivatives
E. Block
33.1.1s Product Subclass 15: 2,3,4,5 Tetrahydrothiepins, Larger Rings,
and Derivatives 259
33.1.15.1 Synthesis of Product Subclass 15 259
33.1.15.1.1 Synthesis by Ring Closure Reactions 259
33.1.15.1.1.1 Method 1: Synthesis from 1,6 Bis(acylsilanes) 259
33.1.15.1.1.2 Method 2: Cyclopalladation of Benzyl Methyl Sulfide 259
33.1.15.1.1.3 Method 3: Synthesis from Diphenylthiirene 1,1 Dioxideand
l Cyclohex 1 enylpyrrolidine 260
33.1.15.1.1.4 Method 4: Synthesis from 1 (Arylsulfonyl) 6 halopent 1 enyl
Methyl Sulfides 260
33.1.15.1.1.5 Method 5: Synthesis from co Halothioacylsilanes 260
33.1.15.1.1.6 Method 6: Synthesis of a 1,2 Dihydro 2 benzothiepin by
Cathodic Reduction of a Benzyl Dithiopivaloate 261
33.1.15.1.2 Synthesis by Ring Transformation 262
33.1.15.1.2.1 Method 1: Ring Enlargement of Three Membered Rings 262
33.1.15.1.2.2 Method 2: Ring Enlargement of Five Membered Rings 263
33.1.15.1.2.2.1 Variation 1: Two Carbon Atom Ring Expansion with
Dimethyl Acetylenedicarboxylate 263
33.1.15.1.2.2.2 Variation 2: [2,3] Sigmatropic Rearrangements of Ylides Obtained from
1 [(Ethoxycarbonyl)methyl] 2 ethynylthiacycloalkanes 263
33.1.15.1.2.3 Method 3: Ring Enlargement of Six Membered Rings 264
33.1.15.1.2.3.1 Variation 1: Two Carbon Atom Ring Expansion with
Dimethyl Acetylenedicarboxylate 264
33.1.15.1.2.3.2 Variation 2: Reaction of 6 Acyl 3,6 dihydro 2H thiopyrans with
Zinc/Chlorotrimethylsilane 265
33.1.15.1.2.3.3 Variation 3: [2,3] Sigmatropic Rearrangements of 1 [(Ethoxycarbonyl)
methyl] 2 ethynylthiepane Sulfonium Ylides 265
33.1.15.1.2.3.4 Variation 4: Rearrangement of Bicyclic Sulfonium Ylides 266
33.1.15.1.2.3.5 Variation 5: Pyrolyses of Sulfoxides 266
33.1.15.1.2.4 Method 4: Ring Enlargement of Seven Membered Rings 267
33.1.15.1.2.4.1 Variation 1: [2,3] Sigmatropic Rearrangement of 1 [(Ethoxycarbonyl)
methyl] 2 ethynylthiocane Sulfonium Ylides 267
33.1.15.1.3 Elimination Reactions Leading toThiacyclohept 2 enes, Thiacyclooct 2 enes,
and Related Systems 267
33.1.15.1.3.1 Method 1: Ring Opening Reactions of Thiaoxabicyclo[3.2.1 ]octanes
andThiaoxabicyclo[3.3.1]nonanes 267
33.1.15.1.3.2 Method 2: Pummerer Reactions 269
33.1.15.1.4 Synthesis by Substituent Modification 270
33.1.15.1.4.1 Substitution of Hydrogen 270
33.1.15.1.4.1.1 Method!: Lithiation of 2,3,4,5 Tetrahydrothiepin 1 Oxide 270
33.1.15.1.4.1.2 Method 2: Allylic Bromination of 4,5 Dihydrothiepin 1,1 Dioxide 270
XXIV Table of Contents
33.1.15.1.4.2 Substitution of Metals 270
33.1.15.1.4.2.1 Method 1: Replacement of Lithium by Alkyl and Hydroxyalkyl Croups 270
33.1.15.1.4.3 Addition Reactions 271
33.1.15.1.4.3.1 Method 1: Oxidation of the Sulfur Atom 271
33.2 Product Class 2: Alk 1 enyl Selenium Compounds
D. Avilov and D. Dittmer
33.2 Product Class 2: Alk 1 enyl Selenium Compounds 275
33.2.1 Product Subclass 1: Alk 1 enyl Selenones 275
33.2.1.1 Synthesis of Product Subclass 1 275
33.2.1.1.1 Method 1: Oxidation of Alk 1 enyl Selenides 275
33.2.2 Product Subclass 2: Alk 1 enyl Selenoxides 276
33.2.2.1 Synthesis of Product Subclass 2 276
33.2.2.1.1 Method 1: Oxidation of Alk 1 enyl Selenides 276
33.2.3 Product Subclass 3: Alk 1 eneselenols 277
33.2.3.1 Synthesis of Product Subclass 3 277
33J.3.1.1 Method 1: Reaction of Divinyl Diselenides with Tributyltin Hydride 277
33.2.4 Product Subclass 4: Metal Alk 1 eneselenolates 277
33.2.4.1 Synthesis of Product Subclass 4 278
33.2.4.1.1 Method 1: Reaction of Metal Complexes with 1,2,3 Selenadiazoles 278
33.2.4.1.2 Method 2: Addition of Metal Complexes Containing Selenium Ligands
to Alkynes 279
33.2.4.1.3 Method 3: Exchange of Selenolate Ligands in Metal Complexes 279
33.2.4.1.4 Methods 4: Other Methods 280
33.2.5 Product Subclass 5: Alk 1 enyl Selenides 280
33.2.5.1 Synthesis of Product Subclass 5 281
33J.5.1.1 Method 1: Coupling of Organoselenenyl Halides or Diorgano Diselenides
with Alk 1 enyl Heteroatom Derivatives 281
33.2.5.1.1.1 Variation 1: Reaction of Organoselenenyl Halides with
Alk 1 enylmagnesium Halides 281
33.2.5.1.1.2 Variation 2: Reaction of Areneselenenyl Halides and Related Compounds
with Alk 1 enylzirconocenes 282
33.2.5.1.1.3 Variation 3: Reaction of an Areneselenenyl Halide with Vinylboronic Acids
and Esters 282
33.2.5.1.1.4 Variation 4: Reaction of Areneselenenyl Halides with
Alk 1 enyl(trialkyl)stannanes and Related Reactions 283
33.2.5.1.1.5 Variation 5: Reaction of Areneselenenyl Halides and Related Compounds
with Alk 1 enyllithiums 283
33.2.5.1.2 Method 2: Coupling of Metal Selenides or Metal Alkane or Arene
selenolates with Alk 1 enyl Heteroatom Derivatives and
Related Reactions 283
Table of Contents XXV
33.2.5.1.3 Method 3: Addition Elimination of Organoselenium Compounds to
Alkenes 284
33.2.5.1.3.1 Variation 1: Addition Elimination of Organoselenenyl Halidesand
Related Compounds 285
33.2.5.1.3.2 Variation 2: Addition Elimination of Selenols 285
33.2.5.1.4 Method 4: Wittig, Horner Wadsworth Emmons, and Related Reactions
of Selenium Precursors with Carbonyl Compounds 286
33.2.5.1.5 Method 5: Addition of Selenium Compounds to Alkynes 287
33.2.5.1.5.1 Variation 1: Addition of Selenols 287
33.2.5.1.5.2 Variation 2: Addition of Arene or Alkaneselenenyl Halides,
Selenosulfonates, and Related Compounds 288
33.2.5.1.5.3 Variation 3: Addition of Diselenides 289
33.2.5.1.5.4 Variation 4: Addition of Other Compounds Containing
a Selenium—Heteroatom Bond 290
33.2.5.1.5.5 Variations 5: Other Variations 291
33.2.5.1.6 Method 6: Addition of Selenium Compounds to Allenes 291
33.2.5.1.7 Method 7: Addition to Alk 1 ynylselenium Compounds 291
33.2.5.1.7.1 Variation 1: Addition to Alk 1 ynyl Selenides 291
33.2.5.1.7.2 Variation 2: Addition to Metal Alk 1 yneselenolates 294
33.2.5.1.8 Method 8: Double Bond Shift of Allyl Selenides and Related Reactions 295
33.2.5.1.9 Methods 9: Other Methods 295
33.2.6 Product Subclass 6: Alk 1 enylselenonium Salts 295
33.2.6.1 Synthesis of Product Subclass 6 295
33.2.6.1.1 Method 1: Alkylation of Alken 1 yl Selenides 295
33.2.6.1.2 Method 2: Addition of Nucleophiles to Alk 1 ynylselenonium Salts 296
33.2.7 Product Subclass 7: Alk 1 enyl Polyselenides 296
33.2.7.1 Synthesis of Product Subclass 7 296
33.2.7.1.1 Method 1: Oxidation of Metal Alk 1 eneselenolates 297
333 Product Class 3: Alk 1 enyl Tellurium Compounds
D. Avilov and D. Dittmer
333 Product Class 3: Alk 1 enyl Tellurium Compounds 303
333.1 Product Subclass 1: Alk 1 enyl /.6 tellanes 303
333.li Synthesis of Product Subclass 1 303
333.1.1.1 Method 1: Substitution of Pentaaryltellurium
Trifluoromethanesulfonates 303
333.2 Product Subclass 2: Alk 1 enyl Telluroxides 304
333.2.1 Synthesis of Product Subclass 2 304
333.2.1.1 Method 1: Addition of Benzenetellurinyl Trifluoromethanesulfonate
to Alkynes 304
333.2.1.2 Method 2: Oxidation of Alk 1 enyl Tellurides 304
333.3 Product Subclass 3: Alk 1 enyl V tellanes 305
XXVI Table of Contents
333.3.1 Synthesis of Product Subclass 3 305
333.3.1.1 Method 1: Metal Tellurium Exchange 305
333.3.1.2 Method 2: Addition of Halogens to Alk 1 enyl Tellurides 305
333.3.1.3 Method 3: Addition of Tellurium(IV) Halides or Organotellurium
TrihalidestoAlkynes 306
333.3.1.4 Method 4: Exchange of Croups on Tellurium in Alk 1 enyl X4 tellanes ¦•• 307
333.3.2 Applications of Product Subclass 3 in Organic Synthesis 308
333.4 Product Subclass 4: Alk 1 enyl Tellurides 308
333.4.1 Synthesis of Product Subclass 4 308
333.4.1.1 Method 1: Coupling of Organotellurenyl Halides or Diorganoditellanes
with Alk 1 enyl Anions or Radical Equivalents 308
333.4.1.1.1 Variation 1: Reaction of Organotellurenyl Halides with Grignard Reagents 309
333.4.1.1.2 Variation 2: Reaction of Organotellurenyl Halides with Alkynylboranes or
Vinylaluminum Compounds 309
333.4.1.1.3 Variation 3: Reaction of Organotellurenyl Halides with
Alk 1 enyl Zirconocenes 310
333.4.1.1.4 Variation 4: Reaction of Organotellurenyl Halides and Derivatives with
Alk 1 enyl Cuprates or Alk 1 enyl Mercury Derivatives 311
333.4.1.1.5 Variation 5: Reaction of 1,2 Bis[(Z) 2 lithiovinyl]benzene Derivatives
and[(1Z,3Z) 1 Lithio 4 (2 lithiophenyl)buta 1,3 dienyl]
(trimethyl)silane with Tellurium Tetrachloride 312
333.4.1.1.6 Variation 6: Intramolecular Baylis Hillman Reactions of
Organotellurenyl Bromides 313
333.4.1.2 Method 2: Alkylation of Alk 1 enyltelluride Anions 313
333.4.1.3 Method 3: Displacement Reactions on Alk 1 enyl Derivatives by
Telluride Anions 314
333.4.1.4 Method 4: Wittig and Related Reactions 315
333.4.1.5 Method 5: Addition of Tellurium Compounds to Alkynes or Allenes 316
333.4.1.5.1 Variations Addition of Tellurols and Metal Tellurides 316
333.4.1.5.2 Variation 2: Addition of Organotellurenyl Halides and Amides 318
333.4.1.5.3 Variation 3: Free Radical Additions of Tellurium Species 319
333.4.1.5.4 Variation 4: Addition of Iron Telluride Complexes 320
333.4.1.6 Method 6: Reductions of Tellurium Compounds 320
333.4.1.6.1 Variations Reduction of Alk 1 enyl Telluroxides 320
333.4.1.6.2 Variation 2: Reduction of Alk 1 enyltellurium Halides 321
333.4.1.6.3 Variation 3: Reduction of Alk 1 enylditellanes 322
333.4.1.6.4 Variation 4: Reduction of Alkynyl Tellurides 322
333.4.1.7 Method 7: Additions to Alkynyl Tellurides 322
333.4.1.8 Method 8: Modifications of Existing Alk 1 enyl Tellurium Species 323
333.4.1.8.1 Variation 1: Addition Reactions to the C=C Bond of Alk 1 enyl Tellurides 323
333.4.1.8.2 Variation 2: Replacement or Modification of Substituents on
the C=C Bond of Alk 1 enyl Tellurides 324
333.4.1.9 Methods 9: Other Methods 326
333.4.2 Applications of Product Subclass 4 in Organic Synthesis 327
333.5 Product Subclass 5: Alk 1 enyltelluronium Salts 328
333.5.1 Synthesis of Product Subclass 5 328
Table of Contents XXVII
333.5.1.1 Method 1: Alkylation of Alk 1 enyl Tellurides 328
333.5.1.2 Method 2: Displacement of Stannanes, Boronic Acids,
and lodophenyl Croups 328
333.6 Product Subclass 6: Dialk 1 enylditellanes 329
333.6.1 Synthesis of Product Subclass 5 329
333.6.1.1 Method 1: Oxidation of Alk 1 enyl Metal Tellurides 329
333.6.1.2 Methods 2: Other Methods 329
33.4 Product Class 4: Alk 1 enyl Nitrogen Compounds
33.4.1 Product Subclass 1:1 Nitroalkenes
N. Ono
33.4.1 ProductSubclass1:1 Nitroalkenes 337
33.4.1.1 Synthesis of Product Subclass 1 337
33.4.1.1.1 Methodi: Nitration of Alkenes 337
33.4.1.1.1.1 Variation 1: Nitration of Vinylsilanes or Vinylstannanes 342
33.4.1.1.1.2 Variation 2: Nitration of a,p Unsaturated Carboxylic Acids 343
33.4.1.1.2 Method 2: Oxidation of Oximes and Amines 344
33.4.1.1.3 Method 3: Elimination Reactions of P Substituted Nitro Compounds •¦• 345
33.4.1.1.3.1 Variation 1: Dehydration of P Nitro Alcohols 346
33.4.1.1.3.2 Variation 2: Elimination of Acids from P Nitro Esters 350
314.1.1.3.3 Variation 3: Elimination of HX from P Nitro Halides 353
33.4.1.1.3.4 Variation 4: Wittig Type Reaction 354
3^4.1.1.3.5 Variation 5: Elimination from P Nitro Sulfides and Sulfoxides 355
314.1.1.3.6 Variation 6: Elimination from a Nitro Selenoxides and P Nitro Selenoxides 356
33.4.1.1.4 Method 4: Synthesis from a Nitro Ketones 357
33.4.1.1.4.1 Variation 1: Synthesis of P Nitroenamines and P Nitrovinyl Sulfides 359
314.1.1.5 Method 5: Addition Elimination Reactions of Nitroalkenes 360
33.4.1.1.5.1 Variation 1: Using Carbon Nucleophiles 360
33.4.1.1.5.2 Variation 2: Using Heteroatom Nucleophiles 365
33.4.2 Product Subclass 2:1 Nitrosoalkenes
H. U. Reissig and R. Zimmer
33.4.2 Product Subclass 2:1 Nitrosoalkenes 371
33.4.2.1 Synthesis of Product Subclass 2 371
33.4.2.1.1 Methodi: Nitrosation Reactions 371
314.2.1.M Variations Nitrosation of Alkenes 371
314.2.1.1.2 Variation 2: Nitrosation of Alkynes 372
33.4.2.1.1.3 Variation 3: Nitrosation of Allenes 372
314.2.1.2 Method 2: Elimination Reactions 372
33.4.2.1.2.1 Variation 1: Dehydrohalogenation of a Halooximes 372
XXVIII Table of Contents
33.4.2.1.2.2 Variation 2: Elimination of Trialkylsilanol from Silyl Nitronates 373
33.4.2.1.2.3 Variation 3: Elimination of Nitrous Acid 374
33.4.2.1.2.4 Variations Elimination of Sulfuric Acid 374
33.4.2.1.3 Method 3: Thermolysis Reactions 375
33.4.2.1.4 Method 4: Photolysis Reactions 375
33.4.2.1.5 Method 5: Reductions of Nitroalkenes 376
33.4.2.1.5.1 Variation 1: Electrochemical Reduction 376
33.4.2.1.5.2 Variation 2: Reduction with Phosphorus Compounds 376
33.4.2.1.6 Method 6: Oxidation Reactions 377
33.4.2.1.7 Method 7: Ring Opening Reactions 377
33.4.2.1.7.1 Variation 1: From Epoxides 377
33.4.2.1.7.2 Variation 2: From Isoxazoles 378
33.4.2.1.8 Method 8: Isomerization Reactions 378
33.4.2.1.9 Method 9: Skeletal Rearrangement Reactions 379
33.4.2.1.10 Method 10: Alkylations of Oximes 379
33.4.2.1.11 Method 11: Derivatization of Stable Nitrosoalkenes 380
33.4.2.2 Applications of Product Subclass 2 in Organic Synthesis 381
33.4.2.2.1 Method 1: Reactions with Nucleophiles 381
33.4.2.2.2 Method 2: Synthesis of a,p Unsaturated Oximes 382
33.4.2.2.3 Method 3: [4+2] Cycloadditions 383
33.4.2.2.4 Method 4: Electrocyclic Ring Closure Reactions 385
33.4.3 Product Subclass 3: W Alk 1 enyliminosulfur Compounds
H. U. Reissig and R. Zimmer
33.4.3 Product Subclass 3: N Alk 1 enyliminosulfur Compounds 391
33.4.3.1 Synthesis of Product Subclass 3 391
33.4.3.1.1 Method 1: Reaction of P Alkoxy Michael Acceptors with
Sulfoximides and Sulfodiimines 391
33.4.3.1.1.1 Variation 1: Reactions with Sulfoximides 391
33.4.3.1.1.2 Variation 2: Reactions with Sulfodiimines 392
33.4.3.1.2 Method 2: Reaction of Alkynes with Dialkylsulfoxonium Salts 392
33.4.3.1.3 Method 3: Reaction of Ethyl Bromoacetate with Sulfoximides 393
33.4.3.1.4 Method 4: Reaction of 4 Amino 1,2 dihydropyrazol 3 one with
Thionyl Chloride 393
33.4.4 Product Subclass 4: Alk 1 enediazonium Salts, Alkeneazoxy,
and Alkeneazo Compounds
33.4.4 Product Subclass 4: Alk 1 enediazonium Salts, Alkeneazoxy,
and Alkeneazo Compounds 395
Table of Contents XXIX
33.4.5 Product Subclass 5: N Alk 1 enyliminophosphorus Compounds
H. U. Reissig and R. Zimmer
33.4.5 Product Subclass 5: N Alk 1 enyliminophosphorus Compounds 397
33.4.5.1 Synthesis of Product Subclass 5 397
33.4.5.1.1 Method 1: Reactions of P Alkoxy Michael Acceptors with Triphenyl
phosphine Imide 397
33.4.5.1.2 Method 2: Reactions of Azides with Triarylphosphines and
Triorganyl Phosphites 397
33A5.1.2.1 Variation 1: With Triarylphosphines 398
33.4.5.1.2.2 Variation 2: With Triorganyl Phosphites 398
33.4.5.1.3 Method 3: Reactions of Nitriles with Triarylphosphines 399
33.4.5.1.4 Method 4: Reactions of Heterocycles Bearing P Acceptor Substituted
Enamine Moieties with Triarylphosphines 399
33.4.5.1.5 Method 5: Elimination Reactions of (a Azidoalkyl)benzotriazoles 400
33.4.5.2 Applications of Product Subclass 5 in Organic Synthesis 400
33.4.5.2.1 Method 1: Aza Wittig Reactions 400
33.4.5.2.2 Method 2: Synthesis of Heterocycles 401
33.4.6 Product Subclass 6: Enamines
T. Sammakia, J. A. Abramite, and M. F. Sammons
33.4.6 Product Subclass 6: Enamines 405
33A6.1 Synthesis of Product Subclass 6 405
33.4.6.1.1 Method 1: Condensation of a Ketone or Aldehyde with an Amine 405
33.4.6.1.1.1 Variation 1: Via Benzotriazole Aminals 406
33.4.6.1.1.2 Variation 2: Using Azeotropic Removal of Water 408
33.4.6.1.1.3 Variation 3: By the Action of Protic Acid Catalysis 409
33.4.6.1.1.4 Variation 4: By the Action of Molecular Sieves as Catalysts and Desiccants 410
33.4.6.1.1.5 Variation 5: By the Action of Calcium Chloride as a Desiccant 411
33.4.6.1.1.6 Variation 6: Bythe Action of Titanium(IV) Chloride as a Promoter 412
33.4.6.1.1.7 Variation 7: By the Action of Boron Trifluoride Diethyl Ether Complex as
a Catalyst 413
33.4.6.1.2 Method 2: Oxidative Amination 414
33.4.6.1.3 Method 3: Cross Coupling Reactions 415
33.4.6.1.3.1 Variation 1: Of Bromides 416
33.4.6.1.3.2 Variation 2: Of Chlorides 418
33.4.6.1.3.3 Variation 3: OfSulfonates 419
33.4.6.1.4 Method 4: Substitution and Addition Elimination Reactions 420
33.4.6.1.5 Method 5: Elimination of Hydrogen 421
33.4.6.1.5.1 Variation 1: Dehydrogenation 421
33A6.1.5.2 Variation 2: Transfer Dehydrogenation 421
33.4.6.1.6 Method 6: Elimination of a Metal Hydroxide 422
33.4.6.1.7 Method 7: Addition of Hydrogen 422
33.4.6.1.7.1 Variation 1: Reduction of Enamides 422
XXX Table of Contents
33.4.6.1.7.2 Variation 2: Dissolving Metal Reduction of Aromatic Amines 423
334.6.1.8 Method 8: Hydroamination 423
33.4.6.1.9 Method 9: Addition of Organometallic Reagents to Nitriles 426
334.6.1.10 Method 10: Hydroaminomethylation 428
334.6.1.11 Method 11: Isomerization 429
334.6.1.12 Method 12: Wittig Reaction of Amides 432
334.6.1.13 Method 13: Homer Wittig Reaction of Ketones and Aldehydes 433
334.6.1.14 Method 14: Alkylidenation of Carbonyl Croups via Titanium Carbenes ••• 434
334.6.1.14.1 Variation 1: Using Dialkyltitanocenes 435
334.6.1.14.2 Variation 2: Using Tebbe's Reagent 436
33.4.6.1.14.3 Variation 3: Takai Alkylidenation 436
334.6.1.14.4 Variation 4: Alkylidenation of Amides with Thioacetals Using
a Titanium(ll) Complex 437
33.4.7 Product Subclass 7: Enammonium Salts
T. Sammakia, J. A. Abramite, and M. F. Sammons
334.7 Product Subclass 7: Enammonium Salts 443
33.4.7.1 Synthesis of Product Subclass 7 443
33.4.7.1.1 Method 1: Alkylation of Enamines 443
334.7.1.2 Method 2: Conjugate Addition/Elimination 444
33.4.7.1.3 Method 3: Alkylation/Elimination 445
334.7.1.4 Method 4: Copper Catalyzed SN2' Substitution of Propargyl Chlorides •• 445
334.7.1.5 Methods: Elimination of a Hydrogen Halide or Water 446
33.4.7.1.6 Method 6: Addition of Trialkylammonium Salts to Activated Alkynes • • • 447
334.7.1.7 Method 7: Cyclopropyliminium Ion Rearrangement 447
334.8 Product Subclass 8: N Silylenamines
S.J. Collier
334.8 Product Subclass 8: /V Silylenamines 451
334.8.1 Synthesis of Product Subclass 8 453
334.8.1.1 Method 1: Synthesis from Imines 453
334.8.1.1.1 Variation 1: Direct Silylation of Imines or Enamines 453
334.8.1.1.2 Variation 2: Other Approaches Involving Imines 458
334.8.1.2 Method 2: Synthesis from Nitriles 460
334.8.1.2.1 Variation 1: Nucleophilic Attack on Nitriles 460
334.8.1.2.2 Variation 2: Other Approaches Involving Nitriles 466
334.8.1.3 Method 3: Isomerization Reactions 467
334.8.1.4 Methods 4: Miscellaneous Methods 469
Table of Contents XXXI
33.4.9 Product Subclass 9: W Borylenamines
S.J. Collier
33.4.9 Product Subclass 9: JV Borylenamines 475
33.4.9.1 Synthesis of Product Subclass 9 477
33.4.9.1.1 Method 1: Direct Borylation of Imines (or Enamines) 477
33.4.9.1.2 Method 2: Synthesis from 1,2 Azaborolium Salts 480
33.4.9.1.3 Method 3: Synthesis from Other N Borylenamines 481
33.4.9.1.4 Methods 4: Miscellaneous Procedures 483
33.4.10 Product Subclass 10: N Haloenamines
S.J. Collier
33.4.10 Product Subclass 10: Af Haloenamines 487
33.4.10.1 Synthesis of Product Subclass 10 487
33.4.10.1.1 Method 1: Halogenation of Enamides 487
33.4.10.1.2 Method 2: N Halopyridinones and Related Compounds by
Direct Halogenation 488
33.4.11 Product Subclass 11: (V Alk 1 enylhydroxylamines
S.J. Collier
33.4.11 Product Subclass 11: /V Alk 1 enylhydroxylamines 493
33.4.11.1 Synthesis of Product Subclass 11 494
33.4.11.1.1 Method 1: Conjugate Addition Reactions of Hydroxylamines 494
33.4.11.1.1.1 Variations WithAlkenes 494
33.4.11.1.1.2 Variation 2: WithAlkynes 496
33.4.H.1.2 Method 2: Synthesis from Hydroxylamines and Aldehydes or Ketones 498
33.4.11.1.3 Methods 3: Miscellaneous Methods 500
33.4.12 Product Subclass 12: /V Alk 1 enylaminosulfur Compounds
S.J. Collier
33.4.12 Product Subclass 12: /V Alk 1 enylaminosulfur Compounds 503
33.4.12.1 Synthesis of Product Subclass 12 504
33.4.12.1.1 Method 1: Synthesis from Imines and Enamines and
Electrophilic Sulfur Agents 504
33.4.12.1.2 Method 2: Synthesis from N Sulfonylimines and Related Compounds • • • 505
33.4.12.1.2.1 Variation 1: Through Deprotonation and Quenching of /V Sulfanyl and
N Sulfinylimines 505
33A12.1.2.2 Variation 2: Through Nucleophilic Attack on N Sulfonylimines 506
33^.12.1.3 Method 3: Synthesis from Primary and Secondary Sulfonamides 509
33A12.1.4 Method 4: Synthesis through 1,2 Elimination Reactions of Amines 511
33A12.1.5 Method 5: Synthesis through Cross Coupling Reactions 512
XXXH Table of Contents _.
33.4.12.1.6 Method 6: Synthesis by Isomerization and Rearrangement 515
33.4.12.1.7 Methods 7: Miscellaneous Methods 517
33.4.13 Product Subclass 13: Alk 1 enylhydrazines
S.J. Collier and M. D. McLaws
33.4.13 Product Subclass 13: Alk 1 enylhydrazines 521
33.4.13.1 Synthesis of Product Subclass 13 524
33.4.13.1.1 Method 1: Synthesis from Hydrazines and Carbonyl Compounds 524
33.4.13.1.1.1 Variation 1: Monosubstituted or N,N Disubstituted Hydrazines 524
33.4.13.1.1.2 Variation 2: N,N' Disubstituted Hydrazines or Trisubstituted Hydrazines 526
33.4.13.1.2 Method 2: Synthesis by Conjugate Addition 528
33.4.13.1.2.1 Variation 1: Of Hydrazines to Alkynes 528
33.4.13.1.2.2 Variation 2: Of Hydrazines to p Substituted Alkenes 530
33.4.13.1.3 Methods 3: Miscellaneous Methods 534
33.4.14 Product Subclass 14: Alk 1 enyl Azides
S.J. Collier
33.4.14 Product Subclass 14: Alk 1 enyl Azides 541
33.4.14.1 Synthesis of Product Subclass 14 544
33.4.14.1.1 Method 1: Condensation of Arylaldehydes with a Azido Esters 544
33.4.14.1.2 Method 2: 1,2 Elimination Reactions 549
33.4.14.1.3 Method 3: 1,4 Addition Reactions 553
33.4.14.1.4 Methods 4: Miscellaneous Methods 556
33.4.15 Product Subclass 15: A/ Alk 1 enylaminophosphorus Compounds
S.J. Collier
33.4.15 Product Subclass 15: Af Alk 1 enylaminophosphorus Compounds 565
33.4.1S.1 Synthesis of Product Subclass 15 565
33.4.15.1.1 Method 1: Synthesis from Imines or Enamines and
Phosphorus Electrophiles 565
33.4.15.1.2 Method 2: Synthesis from Phosphamides and Aldehydes 567
33.4.15.1.3 Method 3: Synthesis from N AllylphosphoricTriamides 569
33.4.15.1.4 Method 4: Synthesis from Nitriles 571
33.4.15.1.5 Methods 5: Miscellaneous Methods 572
33.4.1 e Product Subclass 16:1,2 Oihydroazetes and Derivatives
P. Jubault, E. Leclerc, and J. C. Quirion
33.4.16 Product Subclass 16:1,2 Dihydroazetes and Derivatives 577
314.16.1 Synthesis of Product Subclass 16 577
33.4.16.1.1 Synthesis by Ring Closure Reactions 577
Table of Contents XXXIII
33.4.16.1.1.1 Method 1: Addition of Amines to a Perfluoroenone 577
33.4.16.1.1.2 Method 2: Addition of Amines to Hexafluoropropene Trimers 578
33.4.16.1.1.3 Method 3: [2 + 2] Cycloaddition between an Imine and a Ketene Aminal 579
33.4.16.1.2 Elimination Reactions from Azetidines 579
33.4.16.1.2.1 Method 1: Elimination of a Methanesulfonate Croup 579
33.4.16.1.2.1.1 Variation 1: Synthesis of N Acyl 1,2 dihydroazetes 579
33.4.16.1.2.1.2 Variation 2: Synthesis of N Mesyl and N Nitro 1,2 dihydroazetes 580
33.4.16.1.2.2 Method 2: 1,2 Photoaromatization Reaction of
an Azabicyclohexane Type Diels Alder Adduct 580
33.4.16.1.3 Synthesis by Substituent Modification 581
33.4.16.1.3.1 Addition Reactions 581
33.4.16.1.3.1.1 Method 1: Addition of Malonate Derivatives to Azetes 581
33.4.17 Product Subclass 17: 2,3 Dihydro 1 H pyrroles and Derivatives
P. Jubault, E. Leclerc, and J. C. Quirion
33.4.17 Product Subclass 17:2.3 Dihydro 1 H pyrroles and Derivatives 583
334.17.1 Synthesis of Product Subclass 17 583
33.4.17.1.1 Synthesis by Ring Closure Reactions 583
33.4.17.1.1.1 Method 1: Addition/Cyclization of Sulfonamide Anions with
AlkynyliodoniumTrifluoromethanesulfonates 583
33.4.17.1.1.2 Method 2: lodocyclization of Alk 3 ynylsulfonamides 584
33.4.17.1.1.3 Method 3: Palladium Catalyzed Cyclization of a Propargyl
a Amino Esters 585
33.4.17.1.1.4 Method 4: Ring Closing Metathesis of N Alk 3 enyl
N alk 1 ynylsulfonamides 585
314.17.1.1.5 Method 5: Ring Closing Metathesis of N Alk 3 enylenamines 586
33.4.17.1.2 Elimination Reactions from Pyrrolidines 587
33.4.17.1.2.1 Method 1: Reduction of Lactams Followed by Elimination 587
33.4.17.1.2.2 Method 2: Dehydration of Pyrrolidin 3 ols 591
33.4.17.1.3 Synthesis by Substituent Modification 592
33.4.17.1.3.1 Method 1: Heck Reactions of 2,3 Dihydropyrroles 592
33.4.17.1.3.2 Method 2: Isomerizing Heck Reactions of 2,5 Dihydropyrroles 593
33.4.17.1.3.3 Method 3: Coupling Reactions of Lactam Derived Alkenyl
Trifluoromethanesulfonates 595
33.4.18 Product Subclass 18:1,2 Dihydropyridines, 1,4 Dihydropyridines,
and Derivatives
J. C. Quirion, E. Leclerc, and P. Jubault
33.4.18 Product Subclass 18:1,2 Dihydropyridines, 1,4 Dihydropyridines,
and Derivatives 601
334.18.1 Synthesis of Product Subclass 18 601
XXXIV Table of Contents _.
33.4.18.1.1 Synthesis by Ring Closure Reactions 601
33.4.18.1.1.1 Method!: Three Component Hantzsch Synthesis 601
33.4.18.1.1.1.1 Variation 1: Classical Hantzsch Reaction 601
33.4.18.1.1.1.2 Variation 2: Microwave Activation 602
33.4.18.1.1.1.3 Variation 3: Miscellaneous Approaches 603
33.4.18.1.1.1.4 Variation 4: Solid Phase Hantzsch Synthesis 604
33.4.18.1.1.2 Method 2: Addition/Cyclization of Nitrogen Nucleophiles to
Dicarbonyl Compounds 605
33.4.18.1.1.2.1 Variation 1: Condensation of Amines with Dialdehydes 605
33.4.18.1.1.2.2 Variation 2: Condensation of Amides with Dialdehydes 606
33.4.18.1.1.2.3 Variation 3: Condensation of Ammonia with 1,5 Diketones 606
33.4.18.1.1.3 Method 3: Aza Diels Alder Reaction of 1 Azadienes 607
33.4.18.1.1.4 Method 4: Asymmetric Two Component Hantzsch Reaction 609
33.4.18.1.1.5 Method 5: 6it Electrocyclization of 1 Azatrienes 610
33.4.18.1.2 Synthesis by Ring Transformation 611
33.4.18.1.2.1 Method 1: Rearrangement of a 3,6,7 Triazatricyclo[3.2.1.02 4]octane
Derivative 611
33.4.18.1.2.2 Method 2: Radical Deoxygenation of 3 Azatricyclo[2.2.1.02 6]
heptan 5 ols 612
33.4.18.1.3 Synthesis by Substituent Modification 612
33.4.18.1.3.1 Addition Reactions 612
33.4.18.1.3.1.1 Method 1: Hydride Reductions 612
33.4.18.1.3.1.2 Method 2: Dissolving Metal Reductions 614
33.4.18.1.3.1.3 Method 3: Dithionite Reductions 615
33.4.18.1.3.1.4 Method 4: Addition of Grignard Reagents 615
33.4.18.1.3.1.5 Method 5: Addition of Organotin Reagents 617
33.4.18.1.3.1.6 Method 6: Addition of Organocopper and Organocuprate Reagents — 618
33.4.18.1.3.1.7 Method 7: Addition of Enolates and Enol Ethers 620
33.4.18.1.3.1.8 Method 8: Addition of Other Carbon Nucleophiles 621
33.4.18.1.3.1.9 Method 9: Asymmetric Addition of Nucleophiles to Pyridinium Salts — 622
33.4.18.1.3.1.9.1 Variation 1: Chirality on the Nitrogen Atom 622
33.4.18.1.3.1.9.2 Variation 2: Addition to Chiral Nicotinic Acid Derivatives 624
33.4.18.1.3.1.9.3 Variation 3: Catalytic Asymmetric Reissert Reaction 625
33.4.19 Product Subclass 19:1,2,3,4 Tetrahydropyridines and Derivatives
J. C. Quirion
33.4.19 Product Subclass 19:1,2,3,4 Tetrahydropyridines and Derivatives 629
33.4.19.1 Synthesis of Product Subclass 19 629
33.4.19.1.1 Synthesis by Ring Closure Reactions 629
33.4.19.1.1.1 Method 1: [4+2] Cycloaddition Reactions of 1 Azabutadienes 630
33.4.19.1.1.1.1 Variation 1: Cyclization of N Acyl 2 cyano 1 azabutadienes 630
33.4.19.U.1.2 Variation 2: Cyclization of N Phenyl 2 cyano 1 azabutadienes 631
33.4.19.1.1.1.3 Variation 3: Cyclization of 2 Cyano N (ethoxycarbonyl) 1 azabutadienes 632
Table of Contents XXXV
33.4.19.1.1.2 Method 2: Photochemical Cycloaddition of 3 Aminopropenals and
Alkenes 632
33.4.19.1.1.3 Method 3: Cyclization/lsomerization of 6 Chloroimines 633
33.4.19.1.1.3.1 Variation 1: In Situ Preparation of 8 Chloroimines 633
33.4.19.1.1.3.2 Variation 2: Cyclization after Isolation of 6 Chloroimines 633
33.4.19.1.1.3.3 Variation 3: Nucleophile lnduced Cyclization of 5 Chloroimines 634
33.4.19.1.1.4 Method 4: Intramolecular Cyclization of Aminoaldehydes and
Derivatives 635
33.4.19.1.1.4.1 Variation 1: Intramolecular Cyclization of AminoAcetals 635
33.4.19.1.1.4.2 Variation 2: Intramolecular Cyclization of an Amide and an Aldehyde or
Acetal 636
33.4.19.UA3 Variation 3: Intramolecular Cyclization of Carbamates and Aldehydes — 637
33.4.19.1.1.4.4 Variation 4: Intramolecular Condensation of Tosylamines and Acetals ••• 638
33.4.19.1.1.5 Method 5: Palladium Induced Intramolecular Cyclization of an
(o Alkenic Tosylamide 639
334.19.1.1.6 Method 6: Transition Metal Catalyzed Cyclization 639
33.4.19.1.1.6.1 Variation 1: Platinium Mediated Cycloisomerization of Ene Ynamides •¦• 639
334.19.1.1.6.2 Variation 2: Ring Closing Metathesis of Ene Ynamides 640
33.4.19.1.1.6.3 Variation 3: Ring Closing Metathesis of Ene Enamides 640
334.19.1.1.7 Method 7: Intramolecular Cyclization of Enamino Esters, Ketones,
or Sulfones 641
334.19.1.1.7.1 Variation 1: Cyclization Involving a Halogen Leaving Group 641
334.19.1.2 Synthesis by Transformation of a Cyclic Substrate 643
334.19.1.2.1 Method 1: Reduction/Elimination of a Lactam 643
334.19.1.2.1.1 Variation 1: Reduction of Unsaturated Lactams 643
334.19.1.2.2 Method 2: Elimination of a Phenylselanyl Group 644
334.19.1.2.3 Method 3: Hydrogenation of Pyridine, Pyridinium Salts,
and Dihydropyridines 644
334.19.1.2.4 Method 4: Hydride Reduction of Pyridines and Dihydropyridines 646
334.19.1.2.5 Method 5: Addition Reactions to 2,3 Dihydropyridinium Salts 647
334.19.1.2.5.1 Variation 1: Addition of Organometallic Compounds 648
334.19.1.2.5.2 Variation 2: Addition of Alcohols, Thiols, and Amines 649
334.19.1.2.5.3 Variation 3: Addition of P Dicarbonyl Anions 650
334.19.1.2.6 Method 6: 2 Carbamoylation of 1,4 Dihydropyridines 650
334.19.1.3 Functionalization of 1,2,3,4 Tetrahydropyridines 651
334.19.1.3.1 Method 1: Carboxymethylation of Substituted
Vinyl Trifluoromethanesulfonates 652
334.19.1.3.2 Method 2: Suzuki Reactions of Vinyl Trifluoromethanesulfonates 653
334.19.1.3.3 Method 3: Functionalization of Boronates 654
334.19.1.3.4 Method 4: Coupling Reactions of Vinyl Phosphates 655
XXXVI Table of Contents
33.4.20 Product Subclass 20: 2,3,4,5 Tetrahydro i H azepines, Larger Rings,
and Derivatives
J. C. Quirion, E. Leclerc, and P. Jubault
33.4.20 Product Subclass 20: 2,3,4,5 Tetrahydro 1 H azepines, Larger Rings,
and Derivatives 659
33.4.20.1 Synthesis of Product Subclass 20 659
33.4.20.1.1 Synthesis by Ring Closure Reactions 659
33.4.20.1.1.1 Method 1: Rhodium Catalyzed Alkene Allene Carbocyclization 659
33.4.20.1.2 Elimination Reactions 660
33.4.20.1.2.1 Method 1: Elimination Reactions of 2 Hydroxyazepanes and Derivatives 660
33.4.20.1.3 Synthesis by Substituent Modification 660
33.4.20.1.3.1 Method 1: Hydrodesulfurization of a Thiolactam Derived Enol Ether — 660
33.4.20.1.3.2 Method 2: Coupling Reactions of Lactam Derived
Vinyl Trifluoromethanesulfonates 661
33.4.20.1.3.3 Method 3: Reduction and Suzuki Coupling Reactions of Lactam Derived
Vinyl Phosphates 662
33.5 Product Class 5: Alk 1 enyl Phosphorus Compounds
33.5.1 Product Subclass 1: Alk 1 enylphosphonic Acids and Derivatives
A. C. Caumont and M. Culea
33.5.1 Product Subclass 1: Alk 1 enylphosphonic Acids and Derivatives 665
33.5.1.1 Synthesis of Product Subclass 1 665
33.5.1.1.1 Method 1: Hydrophosphorylation of Alkynes 665
33.5.1.1.1.1 Variation 1: Metal Catalyzed Hydrophosphorylation 665
33.5.1.1.1.2 Variation 2: Base Catalyzed Hydrophosphorylation 666
333.1.1.2 Method 2: P—C Bond Formation from Dialkyl Phosphonates or
Trialkyl Phosphites and Vinyl Halides 667
33.5.1.1.2.1 Variation 1: Michaelis Arbuzov Type Reaction 668
33.5.1.1.2.2 Variation 2: Metal Catalyzed Reaction of Dialkyl Phosphonates and
Vinyl Halides 668
333.1.1.3 Method 3: Wittig Horner Type Alkenation 669
33.5.1.1.3.1 Variation 1: Deprotonation of Methylenebis(phosphonates) 669
33.5.1.1.3.2 Variation 2: Halogen Lithium Exchange from (Halomethyl)phosphonates 671
33.5.1.1.3.3 Variation 3: Synthesis from (Dialkoxyphosphoryl)phosphoniomethanides 672
33.5.1.1.4 Method 4: Peterson Type Alkenylation 673
333.1.1.4.1 Variation 1: Synthesis from (I Silylalkyl)phosphonates 673
333.1.1.4.2 Variation 2: Synthesis from Alkylphosphonates by In Situ Silylation 673
333.1.1.4.3 Variation 3: Synthesis from Bis silylated Methylphosphonates 674
333.1.1.5 Methods: Other Alkenation Reactions 675
333.1.1.5.1 Variation 1: Synthesis from a Stannylated Carbanions 675
Table of Contents XXXVII
33.5.1.1.5.2 Variation 2: Synthesis from a Sulfinyl Carbanions 676
33.5.1.1.6 Method 6: Knoevenagel Type Reactions 677
33.5.1.1.6.1 Variation 1: Using an Aldehyde and a Base Titanium(IV) Chloride System 677
33.5.1.1.6.2 Variation 2: Using Bis aminals and a Haloacetic Acids 678
33.5.1.1.6.3 Variation 3: Using Aldehydes and Tributylarsine 679
33.5.1.1.7 Method 7: Mannich Type Reaction 679
33.5.1.1.8 Method 8: Oxidative Elimination of Sulfanyl or Selanyl Moieties 680
33.5.1.1.9 Method 9: Elimination from P Heteroatom Substituted
Alkylphosphonates 680
33.5.1.1.9.1 Variation 1: Dehydrohalogenation 680
33.5.1.1.9.2 Variation 2: Dehydration 681
33.5.1.1.9.3 Variation 3: Elimination of Nitrous Acid 681
33.5.1.1.10 Method 10: Hydrogenation of Alk 1 ynylphosphonates 682
33.5.1.1.11 Method 11: 1,4 Addition of Nucleophiles to Alk 1 ynylphosphonates •••• 683
33.5.1.1.12 Method 12: Synthesis from Organometallic Intermediates Generated
from Alk 1 ynylphosphonates 683
33.5.1.1.12.1 Variation 1: Synthesis from (Borylalk i enyl)phosphonates 684
33.5.1.1.12.2 Variation 2: Synthesis from (Phosphorylalk i enyl)copper(l) Compounds 685
33.5.1.1.12.3 Variation 3: Synthesis from (Tellanylalk i enyl)phosphonates 686
333.1.1.12.4 Variation 4: Synthesis from Zirconacyclic and Titanacyclic Phosphonates 686
33.5.1.1.13 Method 13: Modification of the Existing Double Bond in
Alk 1 enylphosphonates 688
33.5.1.1.13.1 Variation 1: Metal Catalyzed Cross Coupling Reactions 689
333.1.1.13.2 Variation 2: Alkene Cross Metathesis 690
333.1.1.14 Method 14: Transformation of Alk 1 enylphosphonates into
the Corresponding Phosphonic Acids 690
333.1.1.14.1 Variation 1: Acidic Hydrolysis 691
333.1.1.14.2 Variation 2: Using Bromotrimethylsilane 691
333.2 Product Subclass 2: Alk 1 enylphosphinic Acids and Derivatives
A. C. Caumont and M. Gulea
333.2 Product Subclass 2: Alk 1 enylphosphinic Acids and Derivatives 695
333.2.1 Synthesis of Product Subclass 2 695
333.2.1.1 Method 1: Hydrophosphinylation of Alkynes 695
333.2.1.2 Method 2: Synthesis from Alkylphosphonochloridoates and
Vinylic Organometallic Compounds 697
333.2.1.3 Method 3: Metal Catalyzed Phosphorus Carbon
Cross Coupling Reactions 697
333.2.1.4 Method 4: Alkenylation Reactions 698
33.5.2.1.5 Method 5: Elimination from P Heteroatom Substituted
Alkylphosphinic Esters 699
XXXVIII Table of Contents
33.5.3 Product Subclass 3: Alk 1 enylphosphine Oxides and Derivatives
A. C. Gaumont and M. Gulea
33.5.3 Product Subclass 3: Alk 1 enylphosphine Oxides and Derivatives 701
33.S.3.1 Synthesis of Product Subclass 3 701
33.5.3.1.1 Method 1: Hydrophosphinylation of Alkynes 701
33.5.3.1.2 Method 2: Metal Catalyzed Phosphorus Carbon
Cross Coupling Reaction 702
33.5.3.1.3 Method 3: Alkenation Reactions 703
33.5.3.1.4 Method 4: Elimination from a Oxygenated Alkylphosphine Oxides 704
33.5.3.1.4.1 Variation 1: From (1 Hydroxyalkyl)phosphine Oxides 704
33.5.3.1.4.2 Variation 2: From (1,2 Epoxyalkyl)phosphine Oxides 704
333.3.1.5 Method 5: Elimination from P Heteroatom Substituted
Alkylphosphine Oxides 705
333.3.1.6 Method 6: Nucleophilic 1,4 Addition to Alk 1 ynylphosphine Oxides — 705
3333.1.7 Method 7: Synthesis from Organometallic Intermediates Generated
from Alk 1 ynylphosphine Oxides 706
333.3.1.8 Method 8: Modification of an Existing Double Bond 707
333.3.1.9 Method 9: Oxidation of Alk 1 enylphosphines 708
33.5.3.1.10 Method 10: Acidic Hydrolysis of P Alk 1 enylphosphinous Amides 709
33.5.4 Product Subclass 4: Alk 1 enylphosphines
A. C. Gaumont and M. Gulea
33.5.4 Product Subclass 4: Alk 1 enylphosphines 711
333.4.1 Synthesis of Product Subclass 4 711
333.4.1.1 Method 1: Hydrophosphination of Alkynes with Primary or
Secondary Phosphines 711
333.4.1.1.1 Variation 1: Hydrophosphination under Basic Conditions 712
333.4.1.1.2 Variation 2: Radical Catalyzed Hydrophosphination 713
33.5.4.1.1.3 Variation 3: Thermal Hydrophosphination 714
333.4.1.1.4 Variation 4: Metal Catalyzed Hydrophosphination 714
333.4.1.2 Method 2: Metal Catalyzed Phosphorus Carbon
Cross Coupling Reactions 716
333.4.1.2.1 Variation 1: Palladium Catalyzed Phosphorus Carbon
Cross Coupling Reactions 716
333.4.1.2.2 Variation 2: Nickel Catalyzed Phosphorus Carbon
Cross Coupling Reactions 718
333.4.1.3 Method 3: Reaction between Halophosphines and
Vinylic Organometallic Derivatives 719
333.4.1.4 Method 4: Reduction of Phosphorus Compounds 720
333.4.1.4.1 Variation 1: Reduction of Phosphonates and Phosphinates 720
333.4.1.4.2 Variation 2: Reduction of Chlorophosphines 721
333.4.1.5 Methods 5: Miscellaneous Methods 722
Table of Contents XXXIX
333.5 Product Subclass 5: Alk 1 enylphosphonium Salts
A. C. Gaumont and M. Culea
33.5.5 Product Subclass 5: Alk 1 enylphosphonium Salts 725
33.5.5.1 Synthesis of Product Subclass 5 725
33.5.5.1.1 Method 1: Alkenylation of Tertiary Phosphines 725
33.5.5.1.1.1 Variation 1: Nucleophilic Addition of Triphenylphosphine to
Activated Alkynes 725
33.5.5.1.1.2 Variation 2: Metal Catalyzed Addition of Triphenylphosphine to Alkynes 726
33.5.5.1.2 Method 2: Modification of Phosphoranes or Phosphonium Salts 727
33.5.5.1.2.1 Variation 1: Addition Elimination Reactions of Phosphoranes 727
33.5.5.1.2.2 Variation 2: Elimination Addition from Vinylidene Bisphosphonium Salts 727
335.5.1.3 Methods 3: Miscellaneous Methods 728
33.5.6 Product Subclass 6: P Heteroatom Substituted Alk 1 enylphosphines
A. C. Gaumont and M. Gulea
33.5.6 Product Subclass 6: P Heteroatom Substituted Alk 1 enylphosphines ¦¦• 731
335.6.1 Synthesis of Product Subclass 6 731
335.6.1.1 Method 1: Alk 1 enyl(amino)phosphines by Vinylation of
Halophosphines 731
33.5.6.1.1.1 Variation 1: Synthesis from Amino(chloro)phosphines 731
335.6.1.1.2 Variation 2: Synthesis from Amino(chloro)phosphines Generated In Situ 732
335.6.1.2 Method 2: Alk 1 enylphosphonous Diamides by Reaction between
Enamines, Phosphorus Trihalides, and Amines 733
335.6.1.3 Method 3: Alk 1 enylphosphonous Dihalides by the Reaction of
Phosphorus Trihalides and Organometallic Derivatives 734
335.6.1.4 Method 4: Alk 1 enyl(halo)phosphines by the Reaction of
Tungsten Phosphinidene Complexes and Chloroalkenes — 734
335.7 Product Subclass 7:1,2 Dihydrophosphetes and Derivatives
Gy. Keglevich and H. Szelke
33.5.7 Product Subclass 7:1,2 Dihydrophosphetes and Derivatives 737
335.7.1 Synthesis of Product Subclass 7 737
335.7.1.1 Synthesis by Ring Closure Reactions 737
335.7.1.1.1 Method 1: Ring Fused 1,2 Dihydrophosphetes by Cydoaddition of
1,2 Thiaphospholesand Ynamines 737
335.7.1.1.2 Method 2: A 1 lmino 1,2 dihydro 1 .5 phosphet 1 arnine by Cydo¬
addition of an lmino(methylene)phosphorane and
an Acetylene 738
335.7.1.1.3 Method 3: A 1 lmino 1,2 dihydro U5 phosphet 1 amine by Ring Closure
ofaPhosphabuta 1,3 dieneEffectedbyanAzide 739
335.7.1.1.4 Method 4: Phosphetium Salts of Ring Fused 1,2 Dihydrophosphetes by
Ring Closure of (Arylmethylene)chlorophosphoranes 739
XL Table of Contents
33.5.7.1.1.5 Method 5: Synthesis of a 2 Methylene 1,2 dihydrophosphete via
a Zirconium Containing Tricyclic 1,2 Dihydrophosphete 740
33.5.7.1.2 Synthesis by Ring Transformation 740
33.5.7.1.2.1 Method 1: Ring Expansion of Cycloprop 2 enylidenephosphines with
Azides 740
33.5.7.1.2.2 Method 2: 1,2 Dihydrophosphetes by Titanium Phosphorus Exchange of
a Titanacyclobutene 741
33.5.7.1.2.3 Method 3: A 1,2 Dihydrophosphete 1 Oxide by Ring Contraction of
a 2,3 Dihydro 1,2 thiaphosphole Using Ethanol 742
33.5.8 Product Subclass 8: 2,3 Dihydro 1 H phospholes and Derivatives
Cy. Keglevich and H. Szelke
33.5.8 Product Subclass 8:2,3 Dihydro 1 H phospholes and Derivatives 745
33.5.8.1 Synthesis of Product Subclass 8 745
333.8.1.1 Synthesis by Ring Closure Reactions 745
333.8.1.1.1 Method 1: 1 Alkoxy 2,3 dihydro 1 H phospholes via McCormack Cyclo
addition of Phosphorous Acid Derivatives and Buta 1,3 dienes 745
33.5.8.1.1.1.1 Variation 1: Reaction of Phosphorus Trihalides and Buta 1,3 dienes
Followed by Reaction with Alcohols 745
33.5.8.1.1.1.2 Variation 2: Reaction of a Dichlorophosphite and a Buta 1,3 diene •¦••¦• 746
33.5.8.1.1.2 Method 2: 1 Chloro 4 methyl 2,3 dihydro 1 H phospholes by Reduction
of the Phosphorus Trichloride lsoprene McCormack Cyclo
adduct 747
33.5.8.1.1.3 Method 3: 1 Phenyl 2,3 dihydro 1H phosphole 1 Oxides by McCormack
Reaction of Dichloro(phenyl)phosphine and Buta 1,3 dienes
Followed by Hydrolysis 747
333.8.1.1.4 Method 4: 1 Substituted 2,3 Dihydro 1H phosphole 1 Oxides by
Cyclization of Benzylphosphine Oxides and a,p Unsaturated
Ketones 748
33.5.8.1.1.5 Method 5: 1 Phenyl 2,3 dihydro 1 H phospholes by Intramolecular
Cyclization of But 3 enylchloro(phenyl)phosphines 749
333.8.1.2 Synthesis by Double Bond Rearrangement of 2,5 Dihydro 1H phosphole
Derivatives 749
333.8.1.2.1 Method 1: 1 Methyl 2,3 dihydro 1H phosphole 1 Oxides and Sulfides by
Acid or Base Catalyzed Isomerization 749
333.8.1.2.2 Method 2: A 5 (Diphenylphosphoryl) 2,3 dihydro 1H phosphole 1 Oxide
by Isomerization with Substitution of a 2,5 Dihydro 1H phos
pholei Oxide 750
333.8.1.2.3 Method 3: Annulated 2,3 Dihydro 1 H phospholes by Isomerization with
Substitution of 2,5 Dihydro 1 H phospholes Followed by
Ring Closure 750
333.8.1.2.4 Method 4: 3 Aryl 2,3 dihydro 1 H phosphole 1 Oxides by Isomerization
with Arylation of 2,5 Dihydro 1 H phosphole 1 Oxides 751
Table of Contents XLI
333.8.1.2.5 Method 5: 3 Bromo 1 phenyl 2,3 dihydro 1H phosphole 1 Oxide by
Isomerization with Bromination of 1 Phenyl 2,5 dihydro
1H phosphole1 Oxide 751
335.8.1.2.6 Method 6: 4 Methoxy 1 methyl 2,3 dihydro 1H phosphole 1 Oxide by
Isomerization with Chloro Substitution of 3 Chloro 1 methyl
2,5 dihydro 1H phosphole 1 Oxide 752
33.5.8.1.3 Synthesis by Elimination Reactions 752
335.8.1.3.1 Method 1: 2,3 Dihydro 1H phosphole 1 Oxides by Base Catalyzed R
earrangement of 6 Oxa 3 phosphabicyclo[3.1.0]hexanes — 752
33.5.8.1.3.2 Method 2: A 3 Substituted 2,3 Dihydro 1H phosphole 1 Oxide by
Reaction of a 6 Oxa 3 phosphabicyclo[3.1.0]hexane with
a Malonic Ester Derivative 753
335.8.1.3.3 Method 3: A 2,3 Dihydro 1H phosphole 1 Oxide by Dehydration of
a 2,3,4,5 Tetrahydro 1H phosphol 2 ol 1 Oxide 753
335.8.1.4 Synthesis by Double Bond Rearrangement of Phosphole Derivatives 754
33.5.8.1.4.1 Method 1: 3 Methylene 2,3 dihydro 1H phosphole Sulfides by
Isomerization of 3 Methyl 1H phosphole 1 Sulfides 754
335.8.1.4.2 Method 2: 3 Methylene 2,3 dihydro 1H phosphole 1 Oxides by
Thallium Ethoxide Mediated Conversion of 1 Benzyl
3 methyl 1H phospholium Salts 754
335.8.1.5 Synthesis of Fused 2,3 Dihydro 1H phospholes by Cyclopropanation of
lH Phospholes 755
335.8.1.5.1 Method 1: 2 Phosphabicyclo[3.1.0]hex 3 ene 2 Oxides by
Cyclopropanation of 1 H Phospholes with Diazomethane — 755
33.5.8.1.5.2 Method 2: A 2 Phosphabicyclo[3.1.0]hex 3 ene 2 Oxide by Intra¬
molecular Cyclopropanation of a 1 (lodomethyl)phos
pholium Salt 756
335.8.1.5.3 Method 3: 2 Phosphabicyclo[3.1.0]hex 3 ene 2 Sulfides by Cyclo¬
propanation of 1H Phosphole 1 Sulfides with Ethyl
Diazoacetate 756
335.9 Product Subclass 9:1,2,3,4 Tetrahydrophosphinines and Derivatives
Gy. Keglevich and H. Szelke
33.5.9 Product Subclass 9:1,2,3,4 Tetrahydrophosphinines and Derivatives • • ¦ • 759
335.9.1 Synthesis of Product Subclass 9 759
335.9.1.1 Synthesis by Ring Closure Reactions 759
335.9.1.1.1 Method 1: 1,2,3,4 Tetrahydrophosphinines by Cycloaddition of an
In Situ Formed Phosphabuta 1,3 diene and Unsaturated
Esters 759
335.9.1.1.2 Method 2: A 1,2,3,4 Tetrahydrophosphinine 1 Oxide by Cyclization of
a Diallylphosphine Oxide with Isomerization 759
335.9.1.2 Synthesis by Double Bond Rearrangement of Tetrahydrophosphinines 760
335.9.1.2.1 Method 1: 1,2,3,4 Tetrahydrophosphinines via Bromination of
the Corresponding 1,2,3,6 Tetrahydrophosphinines 760
XUI Table of Contents _„
33.5.9.1.3 Synthesis by Selective Saturation 761
333.9.1.3.1 Method 1: A 1,2,3,4 Tetrahydrophosphinine 1 Oxide by Hydrogenation
of a 1,2 Dihydrophosphinine 1 Oxide 761
333.9.1.3.2 Method 2: A4 (Dichloromethylene) 1,2,3,4 tetrahydrophosphinine
1 Oxide via Hydroboration of the Corresponding 1,4 Dihydro
phosphinine 1 Oxide 761
33.5.9.1.3.3 Method 3: A 1,2,3,4 Tetrahydrophosphinin 4 one 1 Oxide by Hydrolysis
of a X5 Phosphinine 761
33.5.10 Product Subclass 10:1,4 Dihydrophosphinines and Derivatives
Cy. Keglevich and H. Szelke
33.S.10 Product Subclass 10:1,4 Dihydrophosphinines and Derivatives 765
33.5.10.1 Synthesis of Product Subclass 10 765
33.5.10.1.1 Synthesis by Ring Closure Reactions 765
33.5.10.1.1.1 Method 1: 1,4 Dihydrophosphinines by Reaction of 1,4 Diynes with
Arylphosphines 765
335.10.1.1.2 Method 2: 1,4 Dihydrophosphinines by Reaction of Dilithiated
Penta 1,4 dienes with Dichlorophosphines 766
33.5.10.1.2 Synthesis by Ring Transformation 766
33.5.10.1.2.1 Method 1: A Biphosphinin 4(1H) ylidene 1,1' Dioxide by Photolysis of
a 2 Phosphabicyclo[3.1 .Ojhexane Oxide 766
335.10.1.3 Synthesis from X5 Phosphinines and X3 Phosphinines 767
33.5.10.1.3.1 Method 1: 1,4 Dihydrophosphinine 1 Oxides by Isomerization of
X5 Phosphinines 767
33.5.10.1.3.2 Method 2: A 1,4 Dihydrophosphinine 1 Oxide via the Chlorination of
a X3 Phosphinine 767
33.5.10.1.3.3 Method 3: A4 Methylene 1,4 dihydrophosphinine 1 Oxide by
a Lewis Acid Catalyzed Rearrangement of a 4 Methyl
X5 phosphinine 768
335.10.1.3.4 Method 4: 4 Methylene 1,4 dihydrophosphinine 1 Oxides via
Enolization of a X5 Phosphinine 4 carbaldehyde 768
33.5.10.1.3.5 Method 5: A 1',4' Dihydro 2,4' biphosphinine by Special Reaction of
a X3 Phosphinine in the Presence of Lithium 2,2,6,6 Tetra
methylpiperidide 769
335.10.1.4 Synthesis by Substituent Modification 770
335.10.1.4.1 Method 1: A Biphosphinin 4(1H) ylidene 1,1' Dioxide by Coupling of
Two Units of a Phosphinin 4(1H) one 1 Oxide 770
Keyword Index 773
Author Index 817
Abbreviations 861 |
| any_adam_object | 1 |
| any_adam_object_boolean | 1 |
| author | Abramite, J. A. |
| author2 | Molander, Gary A. 1953- |
| author2_role | edt |
| author2_variant | g a m ga gam |
| author_GND | (DE-588)1203386230 (DE-588)117013870 |
| author_facet | Abramite, J. A. Molander, Gary A. 1953- |
| author_role | aut |
| author_sort | Abramite, J. A. |
| author_variant | j a a ja jaa |
| building | Verbundindex |
| bvnumber | BV022192525 |
| classification_rvk | VK 7200 |
| ctrlnum | (OCoLC)634509815 (DE-599)BVBBV022192525 |
| discipline | Chemie / Pharmazie |
| format | Book |
| fullrecord | <?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>00000nam a2200000 cc4500</leader><controlfield tag="001">BV022192525</controlfield><controlfield tag="003">DE-604</controlfield><controlfield tag="005">20240614</controlfield><controlfield tag="007">t</controlfield><controlfield tag="008">061213s2007 a||| |||| 00||| eng d</controlfield><datafield tag="020" ind1=" " ind2=" "><subfield code="a">9783131188519</subfield><subfield code="9">978-3-13-118851-9</subfield></datafield><datafield tag="020" ind1=" " ind2=" "><subfield code="a">9781588904645</subfield><subfield code="9">978-1-58890-464-5</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(OCoLC)634509815</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-599)BVBBV022192525</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-604</subfield><subfield code="b">ger</subfield><subfield code="e">rda</subfield></datafield><datafield tag="041" ind1="0" ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="049" ind1=" " ind2=" "><subfield code="a">DE-355</subfield><subfield code="a">DE-20</subfield><subfield code="a">DE-210</subfield><subfield code="a">DE-19</subfield><subfield code="a">DE-91G</subfield><subfield code="a">DE-188</subfield><subfield code="a">DE-11</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">VK 7200</subfield><subfield code="0">(DE-625)147417:253</subfield><subfield code="2">rvk</subfield></datafield><datafield tag="100" ind1="1" ind2=" "><subfield code="a">Abramite, J. A.</subfield><subfield code="e">Verfasser</subfield><subfield code="4">aut</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Science of synthesis</subfield><subfield code="b">Houben-Weyl methods of molecular transformations</subfield><subfield code="n">33 = Category 4, Compounds with two carbon-heteroatom bonds</subfield><subfield code="p">Ene-X compounds (X=S, Se, Te, N, P)</subfield><subfield code="c">ed. board: D. Bellus ...</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="a">Stuttgart [u.a.]</subfield><subfield code="b">Thieme</subfield><subfield code="c">2007</subfield></datafield><datafield tag="300" ind1=" " ind2=" "><subfield code="a">XLII, 866 Seiten</subfield><subfield code="b">Illustrationen</subfield><subfield code="c">26 cm</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="b">txt</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="b">n</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="b">nc</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="650" ind1="0" ind2="7"><subfield code="a">Organische Synthese</subfield><subfield code="0">(DE-588)4075695-6</subfield><subfield code="2">gnd</subfield><subfield code="9">rswk-swf</subfield></datafield><datafield tag="650" ind1="0" ind2="7"><subfield code="a">Heteroatomare Verbindungen</subfield><subfield code="0">(DE-588)4352909-4</subfield><subfield code="2">gnd</subfield><subfield code="9">rswk-swf</subfield></datafield><datafield tag="689" ind1="0" ind2="0"><subfield code="a">Heteroatomare Verbindungen</subfield><subfield code="0">(DE-588)4352909-4</subfield><subfield code="D">s</subfield></datafield><datafield tag="689" ind1="0" ind2="1"><subfield code="a">Organische Synthese</subfield><subfield code="0">(DE-588)4075695-6</subfield><subfield code="D">s</subfield></datafield><datafield tag="689" ind1="0" ind2=" "><subfield code="5">DE-604</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Bellus, Daniel</subfield><subfield code="e">Sonstige</subfield><subfield code="4">oth</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Molander, Gary A.</subfield><subfield code="d">1953-</subfield><subfield code="0">(DE-588)1203386230</subfield><subfield code="4">edt</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Houben, Josef</subfield><subfield code="d">1875-1940</subfield><subfield code="e">Sonstige</subfield><subfield code="0">(DE-588)117013870</subfield><subfield code="4">oth</subfield></datafield><datafield tag="773" ind1="0" ind2="8"><subfield code="w">(DE-604)BV013247070</subfield><subfield code="g">33</subfield></datafield><datafield tag="776" ind1="0" ind2="8"><subfield code="i">Erscheint auch als</subfield><subfield code="n">Online-Ausgabe</subfield><subfield code="z">978-3-13-183871-1</subfield></datafield><datafield tag="856" ind1="4" ind2="2"><subfield code="m">HBZ Datenaustausch</subfield><subfield code="q">application/pdf</subfield><subfield code="u">http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015404077&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA</subfield><subfield code="3">Inhaltsverzeichnis</subfield></datafield><datafield tag="943" ind1="1" ind2=" "><subfield code="a">oai:aleph.bib-bvb.de:BVB01-015404077</subfield></datafield></record></collection> |
| id | DE-604.BV022192525 |
| illustrated | Illustrated |
| index_date | 2024-07-02T16:21:49Z |
| indexdate | 2024-08-20T00:15:10Z |
| institution | BVB |
| isbn | 9783131188519 9781588904645 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-015404077 |
| oclc_num | 634509815 |
| open_access_boolean | |
| owner | DE-355 DE-BY-UBR DE-20 DE-210 DE-19 DE-BY-UBM DE-91G DE-BY-TUM DE-188 DE-11 |
| owner_facet | DE-355 DE-BY-UBR DE-20 DE-210 DE-19 DE-BY-UBM DE-91G DE-BY-TUM DE-188 DE-11 |
| physical | XLII, 866 Seiten Illustrationen 26 cm |
| publishDate | 2007 |
| publishDateSearch | 2007 |
| publishDateSort | 2007 |
| publisher | Thieme |
| record_format | marc |
| spelling | Abramite, J. A. Verfasser aut Science of synthesis Houben-Weyl methods of molecular transformations 33 = Category 4, Compounds with two carbon-heteroatom bonds Ene-X compounds (X=S, Se, Te, N, P) ed. board: D. Bellus ... Stuttgart [u.a.] Thieme 2007 XLII, 866 Seiten Illustrationen 26 cm txt rdacontent n rdamedia nc rdacarrier Organische Synthese (DE-588)4075695-6 gnd rswk-swf Heteroatomare Verbindungen (DE-588)4352909-4 gnd rswk-swf Heteroatomare Verbindungen (DE-588)4352909-4 s Organische Synthese (DE-588)4075695-6 s DE-604 Bellus, Daniel Sonstige oth Molander, Gary A. 1953- (DE-588)1203386230 edt Houben, Josef 1875-1940 Sonstige (DE-588)117013870 oth (DE-604)BV013247070 33 Erscheint auch als Online-Ausgabe 978-3-13-183871-1 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015404077&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Science of synthesis Houben-Weyl methods of molecular transformations Abramite, J. A. Organische Synthese (DE-588)4075695-6 gnd Heteroatomare Verbindungen (DE-588)4352909-4 gnd |
| subject_GND | (DE-588)4075695-6 (DE-588)4352909-4 |
| title | Science of synthesis Houben-Weyl methods of molecular transformations |
| title_auth | Science of synthesis Houben-Weyl methods of molecular transformations |
| title_exact_search | Science of synthesis Houben-Weyl methods of molecular transformations |
| title_exact_search_txtP | Science of synthesis Houben-Weyl methods of molecular transformations |
| title_full | Science of synthesis Houben-Weyl methods of molecular transformations 33 = Category 4, Compounds with two carbon-heteroatom bonds Ene-X compounds (X=S, Se, Te, N, P) ed. board: D. Bellus ... |
| title_fullStr | Science of synthesis Houben-Weyl methods of molecular transformations 33 = Category 4, Compounds with two carbon-heteroatom bonds Ene-X compounds (X=S, Se, Te, N, P) ed. board: D. Bellus ... |
| title_full_unstemmed | Science of synthesis Houben-Weyl methods of molecular transformations 33 = Category 4, Compounds with two carbon-heteroatom bonds Ene-X compounds (X=S, Se, Te, N, P) ed. board: D. Bellus ... |
| title_short | Science of synthesis |
| title_sort | science of synthesis houben weyl methods of molecular transformations ene x compounds x s se te n p |
| title_sub | Houben-Weyl methods of molecular transformations |
| topic | Organische Synthese (DE-588)4075695-6 gnd Heteroatomare Verbindungen (DE-588)4352909-4 gnd |
| topic_facet | Organische Synthese Heteroatomare Verbindungen |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015404077&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| volume_link | (DE-604)BV013247070 |
| work_keys_str_mv | AT abramiteja scienceofsynthesishoubenweylmethodsofmoleculartransformations33category4compoundswithtwocarbonheteroatombonds AT bellusdaniel scienceofsynthesishoubenweylmethodsofmoleculartransformations33category4compoundswithtwocarbonheteroatombonds AT molandergarya scienceofsynthesishoubenweylmethodsofmoleculartransformations33category4compoundswithtwocarbonheteroatombonds AT houbenjosef scienceofsynthesishoubenweylmethodsofmoleculartransformations33category4compoundswithtwocarbonheteroatombonds |