Science of synthesis: Houben-Weyl methods of molecular transformations 42 = Category 5, Compounds with one saturated carbon-heteroatom bond Organophosphorus compounds (incl. RO-P and RN-P)
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| Format: | Book |
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| Language: | English |
| Published: |
Stuttgart [u.a.]
Thieme
2009
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| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XLV, 1126 S. graph. Darst. 26 cm |
| ISBN: | 9783131189516 9781588905338 |
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| 020 | |a 9783131189516 |9 978-3-13-118951-6 | ||
| 020 | |a 9781588905338 |9 978-1-58890-533-8 | ||
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| 049 | |a DE-355 |a DE-19 |a DE-210 |a DE-91G | ||
| 245 | 1 | 0 | |a Science of synthesis |b Houben-Weyl methods of molecular transformations |n 42 = Category 5, Compounds with one saturated carbon-heteroatom bond |p Organophosphorus compounds (incl. RO-P and RN-P) |c ed. board: D. Bellus ... |
| 264 | 1 | |a Stuttgart [u.a.] |b Thieme |c 2009 | |
| 300 | |a XLV, 1126 S. |b graph. Darst. |c 26 cm | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 700 | 1 | |a Bellus, Daniel |e Sonstige |4 oth | |
| 700 | 1 | |a Houben, Josef |d 1875-1940 |e Sonstige |0 (DE-588)117013870 |4 oth | |
| 773 | 0 | 8 | |w (DE-604)BV013247070 |g 42 |
| 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=017046349&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |3 Inhaltsverzeichnis |
| 943 | 1 | |a oai:aleph.bib-bvb.de:BVB01-017046349 | |
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Titel: Bd. 42. Science of synthesis. Organophosphorus compounds (incl. RO-P and RN-P)
Autor:
Jahr: 2009
Table of Contents
Introduction
F. Mathey
Introduction 1
42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene Complexes
J. C. Slootweg and K. Lammertsma
42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene Complexes - 15
42.1.1 Product Subclass 1: Free Phosphinidenes 15
42.1.1.1 Synthesis of Product Subclass 1 16
42.1.1.1.1 Method 1: Elimination 16
42.1.1.1.1.1 Variation 1: Thermal Generation 16
42.1.1.1.1.2 Variation 2: Photolytic Generation 16
42.1.1.1.2 Method 2: Reduction 17
42.1.1.1.3 Method 3: Phospha-Wittig Reagents 17
42.1.1.2 Applications of Product Subclass 1 in Organic Synthesis 18
42.1.1.2.1 Method 1: Trapping Reactions 18
42.1.2 Product Subclass 2: Neutral Electrophilic Phosphinidene Complexes 19
42.1.2.1 Synthesis of Product Subclass 2 20
42.1.2.1.1 Method 1: Cheletropic Elimination 20
42.1.2.1.1.1 Variation 1: From 7-Phosphanorbornadienes 20
42.1.2.1.1.2 Variation 2: From Phosphiranes 22
42.1.2.1.1.3 Variation 3: From Phosphirenes 22
42.1.2.1.2 Method 2: Salt Metathesis 23
42.1.2.2 Applications of Product Subclass 2 in Organic Synthesis 24
42.1.2.2.1 Method 1: Trapping Reactions 24
42.1.3 Product Subclass 3: Cationic Electrophilic Phosphinidene Complexes 24
42.1.3.1 Synthesis of Product Subclass 3 24
42.1.3.1.1 Method 1: Chloride Abstraction 24
42.1.4 Product Subclass 4: Nucleophilic Phosphinidene Complexes 25
42.1.4.1 Synthesis of Product Subclass 4 25
42.1.4.1.1 Method 1: Salt Metathesis/Elimination 25
42.1.4.1.1.1 Variation 1: Of Metal Hydrides 26
42.1.4.1.1.2 Variation 2: Of Alkali Metal Phosphides 26
42.1.4.1.1.3 Variation 3: Of Transition Metal Phosphides 28
42.1.4.1.2 Method 2: Addition/Elimination 29
42.1.4.1.3 Method 3: Dehydrohalogenation/Ligation 30
42.1.4.1.4 Method 4: cc-Hydrogen Migration 31
42.1.4.1.5 Method 5: Oxidation/Deprotonation 32
42.1.4.2 Applications of Product Subclass 4 in Organic Synthesis 33
42.1.4.2.1 Method 1: Phosphinidene-Transfer Reactions 33
42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and Iminophosphines and
Diphosphenes
M. Yoshifuji
42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and Iminophosphines and
Diphosphenes 37
42.2.1 Product Subclass 1: Oxophosphines 37
42.2.1.1 Synthesis of Product Subclass 1 37
42.2.1.1.1 Method 1: Elimination Reactions 37
42.2.1.1.2 Method 2: Cydoreversion Reactions 38
42.2.2 Product Subclass 2: Thioxophosphines and Selenoxophosphines 39
42.2.2.1 Synthesis of Product Subclass 2 40
42.2.2.1.1 Method 1: Elimination Reactions 40
42.2.2.1.2 Method 2: Cydoreversion Reactions 40
42.2.2.1.3 Methods 3: Miscellaneous Reactions 42
42.2.3 Product Subclass 3: Iminophosphines 44
42.2.3.1 Synthesis of Product Subclass 3 44
42.2.3.1.1 Method 1: Elimination Reactions 44
42.2.3.1.2 Method 2: Substitution Reactions 45
42.2.3.1.3 Method 3: Cycloreversion Reactions 46
42.2.4 Product Subclass 4: Diphosphenes 47
42.2.4.1 Synthesis of Product Subclass 4 47
42.2.4.1.1 Method 1: Elimination and/or Condensation Reactions 47
42.2.4.1.2 Method 2: Rearrangement Reactions 51
42.2.4.1.3 Method 3: Substitution Reactions 52
42.2.5 Product Subclass 5: Heteroatom-Substituted Diphosphenes 53
42.2.6 Product Subclass 6: Stereodefined Diphosphenes 54
42.2.7 Product Subclass 7: Heteroatom-Substituted Iminophosphines 56
42.2.7.1 Synthesis of Product Subclass 7 56
42.2.7.1.1 Method 1: Elimination Reactions 56
42.2.7.1.2 Method 2: Substitution Reactions 58
42.2.8 Product Subclass 8: Tetraphosphenes 58
42.2.8.1 Synthesis of Product Subclass 8 58
42.2.8.1.1 Methodi: Activation of White Phosphorus 58
42.3 Product Class 3: Phosphenium Salts
M. Yoshifuji
423 Product Class 3: Phosphenium Salts 63
42.3.1 Synthesis of Product Class 3 63
«.3.i.i Method 1: Halogen Abstraction of Halophosphines 63
42.3.1.2 Method 2: Alkylation or Protonation of Diphosphenes 66
423.2 Applications of Product Class 3 in Organic Synthesis 67
42.3.2.1 Method 1: Reactions of Phosphenium Cations with Unsaturated
Hydrocarbons 67
42.4 Product Class 4: Alkylphosphines
E. Hey-Hawkins and A. A. Karasik
42.4 Product Class 4: Alkylphosphines 71
42.4.1 Synthesis of Product Class 4 72
42.4.1.1 Method 1: Synthesis from Phosphine, or Primary or Secondary
Phosphines, and Alkyl Halides 73
42.4.1.1.1 Variation 1: From Phosphine and Alkyl Halides 73
42.4.1.1.2 Variation 2: From Primary Phosphines and Alkyl Halides 74
42.4.1.1.3 Variation 3: From Secondary Phosphines and Alkyl or Acyl Halides 75
42.4.1.2 Method 2: Synthesis from Metal Organophosphides and Electrophiles ¦¦• 75
42.4.1.2.1 Variation 1: Synthesis from Metal Organophosphides and Alkyl Halides ••• 75
42.4.1.2.2 Variation 2: Synthesis from Metal Organophosphides and Esters 79
42.4.1.2.3 Variation 3: Ring Opening of Tetrahydrofuran 80
42.4.1.3 Method 3: Addition of Phosphines to C-X Multiple Bonds 81
42.4.1.3.1 Variation 1: Addition to Alk-1-enes or Cyclic Alkenes 81
42.4.1.3.2 Variation 2: Addition to Carbonyl Groups 83
42.4.1.3.3 Variation 3: Mannich-Type Reactions of Phosphines, Formaldehyde,
and Amines 83
42.4.1.4 Method 4: Synthesis from Halophosphines 83
42.4.1.4.1 Variation 1: From Phosphorus Trihalides or Trialkyl Phosphites and
Organometallic Alkali Metal Compounds or Grignard Reagents 83
42.4.1.4.2 Variation 2: From Alkyldihalophosphines and Organometallic Alkali Metal
Compounds or Grignard Reagents 86
42.4.1.4.3 Variation 3: From Dialkylhalophosphines and Organometallic Alkali Metal
Compounds or Grignard Reagents 87
42.4.1.4.4 Variation 4: From Chlorophosphines and Other Organometallic Reagents • 90
42.4.1.5 Method 5: Cleavage of Diphosphines 90
42.4.1.6 Method 6: Synthesis from Elemental Phosphorus and Alkyl Halides,
Alcohols, or Alkenes 91
42.4.1.7 Method 7: Reduction of Halophosphines, Phosphinic Acids, Phosphinic
Acid Esters or Halides, and Trialkyl- and Dialkylphosphine
Oxides 93
42.4.1.7.1 Variation 1: Reduction of Halophosphines with Lithium Aluminum
Hydride or Other Metal Hydrides 93
42.4.1.7.2 Variation 2: Reduction of Alkylphosphonates with Lithium Aluminum
Hydride 94
42.4.1.7.3 Variation 3: Reduction of Dialkylphosphine Oxides, Dialkylphosphinates,
or Alkylphosphonates with Aluminum Derivatives 94
42.4.1.7.4 Variation 4: Reduction of Trialkylphosphine Oxides with Lithium
Aluminum Hydride 97
42.4.1.7.5 Variation 5: Reduction of Dialkylphosphine Oxides, Dialkylphosphinates,
orAlkylphosphinates with Silanes 97
42.4.1.8 Method 8: Reduction of Trialkylphosphine Sulfides and P-Chiral
Phosphine-Borane Complexes Bearing an Alkylsulfanyl Croup 98
42.4.1.8.1 Variation 1: With Alkali Metals 98
42.4.1.8.2 Variation 2: With Lithium Aluminum Hydride 99
42.4.1.9 Method 9: Synthesis from Quaternary Phosphonium Salts 100
42.4.1.9.1 Variation 1: Synthesis from Tetrakis(hydroxymethyl)phosphonium
Halides 100
42.4.1.10 Method 10: Disproportionation of Dialkylphosphine Oxides 101
42.4.1.11 Method 11: Addition Reactions of Unsaturated Tertiary Vinylphosphines • 101
42.4.1.12 Method 12: Enantioselective Cleavage of a P—C Bond in Alkyldimethyl-
phosphine-Borane Complexes 102
42.5 Product Class 5: Bis(alkylphosphino)- and Poly(alkylphosphino)alkanes,
and Di- and Polyphosphines with a P— P Bond
E. Hey-Hawkins and A. A. Karasik
42.5 Product Class 5: Bis(alkylphosphino)- and Poly(alkylphosphino)alkanes,
and Di- and Polyphosphines with a P—P Bond 109
42.5.1 Product Subclass 1: Bis(alkylphosphino)- and
Poly(alkylphosphino)alkanes 109
42.5.1.1 Synthesis of Product Subclass 1 110
42.5.1.1.1 Method 1: Synthesis from Metal Dialkylphosphides and Aliphatic
Electrophiles 110
42.5.1.1.1.1 Variation 1: Synthesis from Dialkylphosphides or Dialkylphosphines
and Polyhaloalkanes 110
42.5.1.1.1.2 Variation 2: Synthesis from Dialkylphosphides and Cyclic Sulfates 115
42.5.1.1.1.3 Variation 3: Synthesis from Dialkylphosphides and (Dialkylphosphino)alkyl
Sulfonates 116
42.5.1.1.1.4 Variation 4: Synthesis from Dialkylphosphines and Polyhaloalkanes,
Alkylarnines, and Alcohols 118
42.5.1.1.1.5 Variations: Synthesis from Alkylphosphides and Dihaloalkanes 119
42.5.1.1.1.6 Variation 6: Synthesis from Bis(alkylphosphides) and Alkyl Halides 120
42.5.1.1.2 Method 2: Synthesis from Metal Phosphinomethanides and
Electrophiles Containing Phosphino Croups 120
42.5.1.1.2.1 Variation 1: Synthesis from (Dialkylphosphino)methanides and
Dialkylhalophosphines 120
42.5.1.1.2.2 Variation 2: Enantioselective Synthesis from Lithium (Dialkylphosphi-
no)methanide-Borane Complexes and Alkylhalophosphines • 122
42.5.1.1.2.3 Variation 3: Synthesis from Poly(dialkylphosphino)methanides and
Dialkylhalophosphines 123
42.5.1.1.2.4 Variation 4: Synthesis from [(Dialkylphosphino)methyl]silanes or
-stannanes and Dialkylhalophosphines 124
42.5.1.1.2.5 Variation 5: Oxidative Coupling of (Dialkylphosphino)methanides 125
42.5.1.1.2.6 Variation 6: Synthesis from (Dialkylphosphino)methanidesand
Polyhaloalkanes or Analogues 127
42.5.1.1.3 Method 3: Synthesis from Halophosphines and Organometallic
Compounds 129
42.5.1.1.3.1 Variation 1: Synthesis from Dialkylhalophosphines and Dimetalated
Alkanes, Alkenes, or Alkynes 129
42.5.1.1.3.2 Variation 2: Synthesis from Bis(halophosphino)alkanes and
Organometallic Compounds 130
42.5.1.1.4 Method 4: Reduction of Phosphine Oxides 132
42.5.1.1.4.1 Variation 1: Reduction of Bis(dialkylphosphoryl)alkanes with Silanes 132
42.5.1.1.4.2 Variation 2: Reduction of Bis(dialkylphosphoryl)alkanes with Lithium
Aluminum Hydride 133
42.5.1.1.5 Method 5: Addition to Double Bonds 135
42.5.1.1.5.1 Variation 1: Addition of Phosphines to Polyenes and Their Heteroatom
Analogues 135
42.5.1.1.5.2 Variation 2: Addition of Dialkylphosphines to Vinyl-or Allylphosphines ••• 137
42.5.1.1.5.3 Variation 3: Addition of Polyphosphinoalkanes to C=CorC=X Bonds •¦•• 139
42.5.1.1.5.4 Variation 4: Addition of Diphosphines to Alkynes 141
42.5.1.1.6 Method 6: Decomposition of Phosphonium Salts 142
42.5.1.1.6.1 Variation 1: Reductive Cleavage of Quaternary Phosphonium Salts 142
42.5.1.1.6.2 Variation 2: Alcoholysis of Quaternary Phosphonium Salts 143
42.5.1.1.7 Method 7: Interconversion of Poly(alkylphosphino)alkanes 143
42.5.1.1.7.1 Variation 1: From Diphosphinomethanides 143
42.5.1.1.8 Method 8: Di- and Oligomerization by Interaction of Functional
Croups of Phosphines 144
42^.1.1.8.1 Variation 1: Di- and Oligomerization of Phosphino Alcohols 144
42.5.2 Product Subclass 2: Tetraalkyldiphosphines and Polyalkylpolyphosphines
with a P-P Bond 145
42.5.2.1 Synthesis of Product Subclass 2 146
42.5.2.1.1 Method 1: Synthesis from Dialkylphosphides or Dialkylphosphines and
Dialkylhalophosphines 146
42.5.2.1.2 Method 2: Coupling of Dialkylphosphine Derivatives 147
42.5.2.1.2.1 Variation 1: Oxidative Coupling of Dialkylphosphines by Transition-Metal
Complexes 147
42.5.2.1.2.2 Variation 2: Reductive Coupling of Dialkylhalophosphines by Alkali
Metals 148
42.5.2.1.3 Method 3: Interconversion of Alkylpolyphosphines 148
42.5.2.1.3.1 Variation 1: Alkylation of Polyphosphide Anions 148
42.5.2.1.3.2 Variation 2: Insertion into P—P Bonds 149
42.6 Product Class 6: Cyclic Phosphines
D. Gudat
42.6 Product Class 6: Cyclic Phosphines 155
42.6.1 Product Subclass 1: Phosphiranes 155
42.6.1.1 Synthesis of Product Subclass 1 156
42.6.1.1.1 Method 1: P-Alkylation of Primary Phosphines 156
42.6.1.1.1.1 Variation 1: From Phosphines or Metal Phosphides and 1,2-Dihalides
or 1,2-Bis(toluenesulfonates) 157
42.6.1.1.1.2 Variation 2: From Metal Phosphides and Oxiranes 159
42.6.1.1.2 Method 2: P-Alkylation of Dichlorophosphines 160
42.6.1.1.3 Method 3: Cycloaddition Reactions 161
42.6.1.1.3.1 Variation 1: From Electrophilic Phosphinidene Complexes and Alkenes ••• 161
42.6.1.1.3.2 Variation 2: From Phosphaalkenes and Diazoalkanes 162
42.6.1.1.3.3 Variation 3: From Phosphaalkenes or Phosphacumulenes and Carbenes
or Carbenoids 164
42.6.1.1.4 Methods 4: Miscellaneous Reactions 166
42.6.2 Product Subclass 2: Phosphetanes 166
42.6.2.1 Synthesis of Product Subclass 2 167
42.6.2.1.1 Method 1: P-Alkylation of Primary Phosphines 167
42.6.2.1.1.1 Variation 1: From Phosphines and 1,3-Dihalides or Derivatives of 1,3-Diols 167
42.6.2.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates 169
42.6.2.1.2 Method 2: P-Alkylation of Dichlorophosphines 171
42.6.2.1.2.1 Variation 1: Lewis Acid Induced Cyclization of Dichlorophosphines
with Alkenes and Subsequent Reduction 171
42.6.2.1.2.2 Variation 2: P-Alkylation of Dichlorophosphines 173
42.6.2.1.3 Method 3: Transformation of Phosphetanes 173
42.6.2.1.3.1 Variation 1: P-Substitution of P-Halophosphetanes 174
42.6.2.1.3.2 Variation 2: C-Substitution of Protected Phosphetanes and Subsequent
Deprotection 174
42.6.2.1.4 Methods 4: Miscellaneous Reactions 176
42.6.3 Product Subclass 3:1,3-Diphosphetanes 176
42.6.3.1 Synthesis of Product Subclass 3 177
42.6.3.1.1 Method 1: Cycloaddition Reactions 177
42.6.3.1.1.1 Variation 1: Cyclodimerization of Phosphaalkenes 177
42.6.3.1.1.2 Variation 2: Cydooligomerization of Phosphaalkynes 178
42.6.3.1.1.3 Variation 3: Oxidative Coupling of Polyphospholides 179
42.6.3.1.2 Methods 2: Miscellaneous Reactions 180
42.6.4 Product Subclass 4: Five- and Six-Membered Rings: Phospholanes,
Phosphinanes, 2,5-Dihydrophospholes, and 1,2,5,6-Tetrahydro-
phosphinines 180
42.6.4.1 Synthesis of Product Subclass 4 181
42.6.4.1.1 Method 1: P-Alkylation of Primary Phosphines 181
42.6.4.1.1.1 Variation 1: From Phosphines and ct.co-Dihalides or Disulfonates of
oc.co-Diols 181
42.6.4.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates 183
42.6.4.1.2 Method 2: Alkylation of Dichlorophosphines or Phosphinic Acid
O,S-Diesters 186
42.6.4.1.2.1 Variation 1: From Dichlorophosphines or Phosphinic Acid 0,5-Diesters
and a,(B-Di-Grignard or Dilithium Reagents 186
42.6.4.1.2.2 Variation 2: From Dichlorophosphines, Alkenes, and Organometallic
Reagents 187
42.6.4.1.3 Method 3: Hydrophosphination of Double Bonds 188
42.6.4.1.3.1 Variation 1: Addition of Phosphines to Alkenes 189
42.6.4.1.3.2 Variation 2: Addition of Phosphine and Primary Phosphines to
1,4-Dien-3-ones 190
42.6.4.1.3.3 Variation 3: Addition of Phosphines to Carbonyl Compounds 192
42.6.4.1.4 Method 4: Cycloaddition or Metathesis Reactions 192
42.6.4.1.4.1 Variation 1: 2,5-Dihydrophospholes from Dihalophosphines and Dienes
via [4+1] Cycloaddition and Reduction 193
42.6.4.1.4.2 Variation 2: 1,2,5,6-Tetrahydrophosphininesfrom Phosphaalkenes and
1,3-Dienes via [4+2] Cycloaddition 195
42.6.4.1.4.3 Variation 3: 7-Phosphanorbornenes from [4+2] Cycloaddition of
Phosphole Derivatives with Dienophiles 196
42.6.4.1.4.4 Variation 4: 2,5-Dihydrophospholes from Diallylphosphines via Alkene
Metathesis 199
42.6.4.1.5 Method 5: Transformation of Cyclic Phosphines 200
42.6.4.1.5.1 Variation 1: Transformation of P-Substituents in Five- and Six-Membered
Heterocycles 200
42.6.4.1.5.2 Variation 2: Lithiation and Electrophilic Substitution at a-C-H Bonds
in Cyclic Phosphine Oxides and Borane Complexes 201
42.6.4.1.6 Methods 6: Miscellaneous Reactions 203
42.6.5 Product Subclass 5: Cyclic Phosphines with Seven-Membered and
Larger Rings 204
42.6.5.1 Synthesis of Product Subclass 5 205
42.6.5.1.1 Methodi: P-Alkylation of Phosphines 205
42.6.5.1.2 Method 2: P-Alkylation of Dihalophosphines 206
42.6.5.1.3 Method 3: P-Alkylation of Tertiary Phosphines or Diphosphines and
Reduction 207
42.6.5.1.4 Method 4: Hydrophosphination of Alkenes and Alkynes 210
42.6.5.1.5 Methods 5: Miscellaneous Reactions 212
42.7 Product Class 7: Dialkylphosphinous Acids and Derivatives
K. M. Pietrusiewicz and M. Stankevic
42.7 Product Class 7: Dialkylphosphinous Acids and Derivatives 221
42.7.1 Product Subclass 1: Dialkylphosphinous Acid Halides 221
42.7.1.1 Synthesis of Product Subclass 1 221
42.7.1.1.1 Methodi: Synthesis from Phosphorous Halides by P—C Bond Formation 221
42.7.1.1.2 Method 2: Ligand Exchange in Dialkylphosphinous Acid Derivatives 222
42.7.1.2 Applications of Product Subclass 1 in Organic Synthesis 223
42.7.2 Product Subclass 2: Dialkylphosphinous Acids 224
42.7.2.1 Synthesis of Product Subclass 2 224
42.7.2.1.1 Method 1: Synthesis from H-Phosphonates by Substitution 224
42.7.2.1.2 Method 2: Hydrolysis of Dialkylphosphinous Acid Derivatives 226
42.7.2.2 Applications of Product Subclass 2 in Organic Synthesis 226
42.7.3 Product Subclass 3: Dialkylphosphinous Acid Esters 227
42.7.3.1 Synthesis of Product Subclass 3 227
42.7.3.1.1 Method 1: Alcoholysis of Dialkylphosphinous Acid Derivatives 227
42.7.3.1.2 Method 2: Synthesis from Phosphorous Acid Monoester Dihalides by
P-C Bond Formation 228
42.7.3.2 Applications of Product Subclass 3 in Organic Synthesis 229
42.7.4 Product Subclass 4: Dialkylthiophosphinous Acids 230
42.7.4.1 Synthesis of Product Subclass 4 230
42.7.4.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Derivatives 230
42.7.4.2 Applications of Product Subclass 4 in Organic Synthesis 230
42.7.5 Product Subclass 5: Dialkylthiophosphinous Acid Esters 231
42.7.5.1 Synthesis of Product Subclass 5 231
42.7.5.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Halides 231
42.7.e Product Subclass 6: Dialkylselenophosphinous Acids 231
42.7.6.1 Synthesis of Product Subclass 6 232
42.7.6.1.1 Method 1: Synthesis from Dialkylphosphines 232
42.7.7 Product Subclass 7: Dialkylselenophosphinous Acid Esters 232
42.7.7.1 Synthesis of Product Subclass 7 232
42.7.7.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Halides 232
42.7.8 Product Subclass 8: Dialkylphosphinous Acid Amides 233
42.7.8.1 Synthesis of Product Subclass 8 233
42.7.8.1.1 Method 1: Aminolysis of Dialkylphosphinous Acid Derivatives 233
42.7.8.1.2 Method 2: Synthesis from Phosphorous Acid Derivatives by P—C Bond
Formation 234
42.7.8.2 Applications of Product Subclass 8 in Organic Synthesis 234
42.8 Product Class 8: Alkylphosphonous Acids and Derivatives
K. M. Pietrusiewicz and M. Stankevic
42.8 Product Class 8: Alkylphosphonous Acids and Derivatives 243
42.8.1 Product Subclass 1: Alkylphosphonous Acid Dihalides 243
?2.8X1 Synthesis of Product Subclass 1 244
42.8.1.1.1 Method 1: Electrophilic Alkylation of Phosphorus Trihalides 244
42.8.1.1.2 Method 2: Nucleophilic Alkylation of Phosphorus Trihalides by
Organometallic Reagents 244
42.8.1.1.3 Method 3: Ligand Exchange Using Alkylphosphines as Substrates 245
42.8.1.2 Applications of Product Subclass 1 in Organic Synthesis 246
42.8.2 Product Subclass 2: Alkylphosphonous Acid Monohalides 247
42.8.2.1 Synthesis of Product Subclass 2 247
42.8.2.1.1 Method 1: Partial Hydrolysis of Alkyl(dihalo)phosphines 247
42.8.3 Product Subclass 3: Alkylphosphonous Acid Monoester Monohalides — 247
42.8.3.1 Synthesis of Product Subclass 3 247
42.8.3.1.1 Method 1: Ligand Exchange in Alkyl(dihalo)phosphines 247
42.8.4 Product Subclass 4: Alkylthiophosphonous Acid Monohalide Monoesters 248
42.8.4.1 Synthesis of Product Subclass 4 248
42.8.4.1.1 Method 1: Ligand Exchange of Alkyl(dihalo)phosphines 248
42.8.5 Product Subclass 5: Alkylphosphonous Acid Monoamide Monohalides • • • 249
42.8.5.1 Synthesis of Product Subclass 5 249
42.8.5.1.1 Method 1: Partial Aminolysis of Alkyl(dihalo)phosphines 249
42.8.5.1.2 Method 2: Ligand Exchange in Alkyl(amino)phosphine Derivatives 250
42.8.6 Product Subclass 6: Alkylphosphonous Acids 251
42.8.6.1 Synthesis of Product Subclass 6 251
42.8.6.1.1 Method 1: Hydrolysis of Alkyl(halo)phosphines 251
42.8.6.1.2 Method 2: Hydrophosphination of Alkenes 252
42.8.6.2 Applications of Product Subclass 6 in Organic Synthesis 252
42.8.7 Product Subclass 7: Alkylphosphonous Acid Monoesters 253
42.8.7.1 Synthesis of Product Subclass 7 253
42.8.7.1.1 Method 1: Alcoholysis of Alkylphosphines 253
42.8.7.1.2 Method 2: Esterification of Monoalkylphosphinic Acids 254
42.8.7.1.3 Method 3: Hydrolysis of Dialkyl Phosphonites and Related Compounds ¦ 255
42.8.7.1.4 Method 4: Hydrophosphination of Alkenes 255
42.8.7.2 Applications of Product Subclass 7 in Organic Synthesis 256
42.8.8 Product Subclass 8: Alkylphosphonous Acid Diesters 256
42.8.8.1 Synthesis of Product Subclass 8 256
42.8.8.1.1 Method 1: Alcoholysis of Alkylphosphonites 256
42.8.8.1.2 Method 2: Synthesis from Halophosphonites 257
42.8.8.2 Applications of Product Subclass 8 in Organic Synthesis 258
42.8.9 Product Subclass 9: Alkylthiophosphonous Acid 5-Monoesters 258
42.8.9.1 Synthesis of Product Subclass 9 258
42.8.9.1.1 Method 1: Hydrolysis of Alkyl(alkylsulfanyl)(halo)phosphines 258
42.8.10 Product Subclass 10: Alkylphosphonous Acid Monoamides 259
42.8.10.1 Synthesis of Product Subclass 10 259
42.8.10.1.1 Method 1: Hydrolysis of Alkyl(diamino)phosphines 259
42.8.11 Product Subclass 11: Alkylthiophosphonous Acid O-Monoesters 259
42.8.11.1 Synthesis of Product Subclass 11 260
42.8.11.1.1 Method 1: Synthesis from Alkyl(alkoxy)(halo)phosphines 260
42.8.12 Product Subclass 12: Alkylthiophosphonous Acid Diesters 260
42.8.12.1 Synthesis of Product Subclass 12 260
42.8.12.1.1 Method 1: Alcoholysis of Alkyl(alkylsulfanyl)(halo)phosphines 260
42.8.13 Product Subclass 13: Alkylphosphonous Acid Monoester Monoamides ¦ • • 261
42^.13.1 Synthesis of Product Subclass 13 261
42.8.13.1.1 Method 1: Alcoholysis of Alkylphosphine Derivatives 261
42.8.13.1.2 Method 2: Aminolysis of Alkylphosphonous Acid Derivatives 262
42.8.13.2 Applications of Product Subclass 13 in Organic Synthesis 262
42.8.14 Product Subclass 14: Alkyldithiophosphonous Acid Diesters 263
42A14.1 Synthesis of Product Subclass 14 263
42.8.14.1.1 Method 1: Synthesis from Primary Alkylphosphines and Disulfides 263
42.8.14.1.2 Method 2: Thioalcoholysis of Alkyl(dihalo)phosphines 263
42.8.15 Product Subclass 15: Alkylthiophosphonous Acid Monoester Monoamides 264
42.8.15.1 Synthesis of Product Subclass 15 264
42.8.15.1.1 Method 1: Thioalcoholysis of Alkyl(diamino)phosphines 264
42.8.16 Product Subclass 16: Alkyldiselenophosphonous Acid Diesters 265
42.8.16.1 Synthesis of Product Subclass 16 265
4Z8.16.1.1 Method 1: Selenoalcoholysis of Alkyl(dihalo)phosphines 265
42.8.17 Product Subclass 17: Alkylphosphonous Acid Diamides 265
42.8.17.1 Synthesis of Product Subclass 17 265
42^.17.1.1 Method 1: Aminolysis of Substituted Alkylphosphines 265
42.8.17.1.2 Method 2: Synthesis from Diamino(halo)phosphines 266
42.8.17.2 Applications of Product Subclass 17 in Organic Synthesis 266
42.9 Product Class 9: Phosphorous Acid and Derivatives
M. Stankevic and K. M. Pietrusiewicz
42.9 Product Class 9: Phosphorous Acid and Derivatives 275
42.9.1 Product Subclass 1: Phosphorous Acid Monoester Dihalides 275
42.9.1.1 Synthesis of Product Subclass 1 275
42.9.1.1.1 Method 1: Alcoholysis of Phosphorus Trihalides 275
42.9.1.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives • 276
42.9.1.2 Applications of Product Subclass 1 in Organic Synthesis 276
42A2 Product Subclass 2: Phosphorothious Acid S-Monoester Dihalides 276
42.9.2.1 Synthesis of Product Subclass 2 277
42.9.2.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides 277
42.9.2.2 Applications of Product Subclass 2 in Organic Synthesis 277
42.9.3 Product Subclass 3: Phosphorous Acid Monoamide Dihalides 277
42.9.3.1 Synthesis of Product Subclass 3 277
42.9.3.1.1 Method 1: Aminolysis of Phosphorus Trihalides 277
42.9.3.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives • 278
42.9.3.2 Applications of Product Subclass 3 in Organic Synthesis 279
42.9.4 Product Subclass 4: Phosphorous Acid Monoester Monohalides 279
42.9.5 Product Subclass 5: Phosphorous Acid Diester Monohalides 279
42.9.5.1 Synthesis of Product Subclass 5 280
42.9.5.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 280
42.9.5.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives ¦ 280
42.9.5.3 Applications of Product Subclass 5 in Organic Synthesis 281
42.9.e Product Subclass 6: Phosphorothious Acid Diester Monohalides 282
42.9.6.1 Synthesis of Product Subclass 6 282
42.9.6.1.1 Method 1: Amine-Halogen Exchange in Phosphorothious Acid Diester
Monoamides 282
42.9.7 Product Subclass 7: Phosphorous Acid Monoester Monoamide Monoha¬
lides 282
42.9.7.1 Synthesis of Product Subclass 7 283
42.9.7.1.1 Method 1: Alcoholysis of Phosphorous Acid Monoamide Dihalides 283
42.9.7.1.2 Method 2: Aminolysis of Phosphorous Acid Monoester Dihalides 283
42.9.7.1.3 Method 3: Consecutive Alcoholysis and Aminolysis of Phosphorus
Trihalides 283
42.9.7.1.4 Method 4: Ligand-Exchange Reactions of Phosphorous Acid Derivatives ¦ 284
42.9.7.2 Applications of Product Subclass 7 in Organic Synthesis 284
42.9.8 Product Subclass 8: Phosphorodithious Acid Diester Monohalides 285
42.9.8.1 Synthesis of Product Subclass 8 285
42.9.8.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides 285
42.9.8.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives ¦ 285
42.9.9 Product Subclass 9: Phosphorothious Acid Monoester Monoamide
Monohalides 286
42.9.9.1 Synthesis of Product Subclass 9 286
42.9.9.1.1 Method 1: Amine-Halogen Exchange in Phosphorothious Acid Diester
Monoamides 286
423.io Product Subclass 10: Phosphorous Acid Diamide Monohalides 287
42.9.10.1 Synthesis of Product Subclass 10 287
423.10.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives 287
423.10.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives ¦ 288
42.9.10.2 Applications of Product Subclass 10 in Organic Synthesis 288
42.9.H Product Subclass 11: Phosphorous Acid Monoesters 288
42.9.11.1 Synthesis of Product Subclass 11 289
42.9.11.1.1 Method 1: Hydrolysis of Phosphorous Acid Esters 289
42.9.11.1.2 Method 2: Synthesis from Other Phosphorous Acid Derivatives 289
42.9.11.1.3 Method 3: Esterification of Phosphorous Acid 290
42.9.11.2 Applications of Product Subclass 11 in Organic Synthesis 291
42.9.12 Product Subclass 12: Phosphorous Acid Diesters (Secondary Phosphites) 291
42.9.12.1 Synthesis of Product Subclass 12 291
42.9.12.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives 291
42.9.12.1.2 Method 2: Alcoholysis of Phosphorous Acid Derivatives 292
42.9.12.1.3 Method 3: Other Syntheses from Phosphorous Acid Derivatives 293
42.9.12.1.4 Method 4: Esterification of Phosphorous Acid Derivatives 293
42.9.12.2 Applications of Product Subclass 12 in Organic Synthesis 294
42.9.13 Product Subclass 13: Phosphorous Acid Triesters (Tertiary Phosphites) - ¦ • 295
42.9.13.1 Synthesis of Product Subclass 13 295
42.9.13.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 295
42.9.13.1.2 Method 2: Transesterification of Phosphorous Acid Triesters 297
42.9.13.2 Applications of Product Subclass 13 in Organic Synthesis 297
42.9.14 Product Subclass 14: Phosphorothious Acid O-Monoesters 298
42.9.14.1 Synthesis of Product Subclass 14 298
42.9.14.1.1 Method 1: Sulfanylation of Phosphorous Acid Diesters 298
42.9.15 Product Subclass 15: Phosphorothious Acid O,O-Diesters 299
42.9.15.1 Synthesis of Product Subclass 15 299
42.9.15.1.1 Method 1: Sulfanylation of Phosphorous Acid Derivatives 299
42.9.15.2 Applications of Product Subclass 15 in Organic Synthesis 300
42.9.16 Product Subclass 16: Phosphorothious Acid Triesters 300
42.9.16.1 Synthesis of Product Subclass 16 300
42.9.16.1.1 Method 1: Alcoholysis of Phosphorothious Acid Derivatives 300
42.9.16.1.2 Method 2: Thioalcoholysis of Phosphorous Acid Derivatives 301
42.9.17 Product Subclass 17: Phosphorodithious Acid S,S-Diesters 301
42.9.18 Product Subclass 18: Phosphorodithious Acid O-Monoesters 301
42.9.19 Product Subclass 19: Phosphorodithious Acid Triesters 302
42.9.19.1 Synthesis of Product Subclass 19 302
42.9.19.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 302
42.9.20 Product Subclass 20: Phosphoroselenous Acid O,O-Diesters 303
42.9.20.1 Synthesis of Product Subclass 20 303
42.9.20.1.1 Method 1: Selanylation of Phosphorous Acid Diester Monohalides 303
42.9.21 Product Subclass 21: Phosphorous Acid Monoester Monoamides 303
42.9.21.1 Synthesis of Product Subclass 21 303
42.9.21.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives 303
42.9.22 Product Subclass 22: Phosphorous Acid Diester Monoamides 304
42.9.22.1 Synthesis of Product Subclass 22 304
42.9.22.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 304
42.9.22.1.2 Method 2: Aminolysis of Phosphorous Acid Derivatives 306
42.9.22.2 Applications of Product Subclass 22 in Organic Synthesis 306
42.9.23 Product Subclass 23: Phosphorothious Acid Diester Monoamides 307
42.9.23.1 Synthesis of Product Subclass 23 307
42.9.23.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 307
42.9.24 Product Subclass 24: Phosphorous Acid Diamides 308
42.9.24.1 Synthesis of Product Subclass 24 308
42.9.24.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives 308
42.9.25 Product Subclass 25: Phosphorous Acid Monoester Diamides 309
42.9.25.1 Synthesis of Product Subclass 25 309
42.9.25.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 309
42.9.25.1.2 Method 2: Aminolysis of Phosphorous Acid Derivatives 310
42.9.25.2 Applications of Product Subclass 25 in Organic Synthesis 311
42.9.26 Product Subclass 26: Phosphorotrithious Acid Triesters 311
42.9.26.1 Synthesis of Product Subclass 26 311
42.9.26.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 311
42.9.27 Product Subclass 27: Phosphorodithious Acid Diester Monoamides 312
42.9.27.1 Synthesis of Product Subclass 27 312
42.9.27.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives 312
42.9.28 Product Subclass 28: Phosphorothious Acid Monoester Diamides 312
42.9.28.1 Synthesis of Product Subclass 28 313
42.9.28.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 313
42.9.29 Product Subclass 29: Phosphorotriselenous Acid Triesters 313
42.9.29.1 Synthesis of Product Subclass 29 313
42.9.29.1.1 Method 1: Reaction of a Diselenide with Elemental Phosphorus 313
42.9.30 Product Subclass 30: Phosphorous Acid Triamides 313
42.9.30.1 Synthesis of Product Subclass 30 314
42.9.30.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives 314
42.9.30.2 Applications of Product Subclass 30 in Organic Synthesis 315
42.10 Applications of Tricoordinated Phosphorus Compounds
in Homogeneous Catalysis
42.10.1 General Catalytic Methods
M. Toffano
42.10.1 General Catalytic Methods 347
42.io.il Formation of C—CBonds 347
42.10.1.1.1 Method 1: Palladium-Promoted Cross-Coupling Reactions 347
42.10.1.1.2 Method 2: Catalysis with Phosphonium Salts as Ligand Precursors 352
42.10.1.2 Formation of C—N Bonds 353
42.10.1.2.1 Method 1: Amination of Aryl and Hetaryl Halides or
Trifluoromethanesulfonates 353
42.10.1.2.2 Method 2: Amination of Alk-1-enyl Halides or
Trifluoromethanesulfonates 360
42.10.1.2.3 Method 3: Intramolecular Amination Reactions 360
42.10.1.3 Formation of C—0 Bonds 361
42.10.1.3.1 Method 1: Alkyl Aryl Ether Synthesis 361
42.10.1.3.2 Method 2: Diaryl Ether Synthesis 362
42.10.1.4 Formation of C—P Bonds 363
42.10.1.4.1 Method 1: Formation of Alkyl phosphorus Compounds 363
42.10.1.4.2 Method 2: Formation of Alkenylphosphorus Compounds 364
42.10.1.4.2.1 Variation 1: Hydrophosphination of Alkynes 364
42.10.1.4.2.2 Variation 2: Coupling Reactions 366
42.10.1.4.3 Method 3: Formation of Alkynylphosphorus Compounds 368
42.10.1.4.4 Method 4: Formation of Arylphosphorus Compounds 368
42.10.1.5 Formation of C—S Bonds 369
42.10.1.5.1 Method 1: Formation of an Aryl-Sulfur Bond 370
42.10.1.5.2 Method 2: Formation of an Alkenyl-Sulfur Bond 370
42.10.1.5.3 Method 3: Formation of an Alkynyl-Sulfur Bond 371
42.10.1.6 Formation of C—Sn Bonds 372
42.10.1.7 Synthesis with Catalyst Recycling 373
42.10.1.7.1 Method 1: Catalysis with Fluorinated Phosphines 373
42.10.1.7.2 Method 2: Catalysis with Water-Soluble Phosphines 374
42.10.1.7.2.1 Variation 1: Catalysis with Sulfonated and Carboxylated Phosphines 375
42.10.1.7.2.2 Variation 2: Catalysis with Phosphines Bearing Ammonium Groups 376
42.10.1.7.2.3 Variation 3: Catalysis with Carbohydrate-Derived Phosphines 377
42.10.1.7.2.4 Variation 4: Catalysis with Polyether Phosphines 377
42.10.1.7.3 Method 3: Catalysis with Polymer-Supported Phosphines 378
42.10.1.7.3.1 Variation 1: Metal-Promoted Catalysis with Polymer-Supported
Phosphines 378
42.10.1.7.3.2 Variation 2: Catalysis with Polymer-Supported Phosphine Reagents 380
42.10.2 Enantioselective Catalytic Methods
J.-C. Fiaud and A. Marinetti
42.10.2 Enantioselective Catalytic Methods 391
42.10.2.1 Approaches to Enantioselective Catalysts 391
42.10.2.1.1 Method 1: Approaches to Chiral Cyclic Phosphines 397
42.10.2.1.1.1 Variation 1: Phospholane-Based Chiral Ligands 397
42.10.2.1.1.2 Variation 2: Phosphetane-Based Chiral Ligands 398
42.10.2.1.1.3 Variation 3: Phosphepin-Based Chiral Ligands 399
42.10.2.1.2 Method 2: Approaches to Atropisomeric Biaryl Bisphosphines 399
42.10.2.1.3 Method 3: Approaches to Ferrocenylphosphines with Planar Chirality •¦• 402
42.10.2.1.4 Method 4: Approaches to Hybrid Phosphorus-Nitrogen Ligands 405
42.10.2.1.4.1 Variation 1: Phosphino-4,5-dihydrooxazole Ligands 405
42.10.2.1.4.2 Variation 2: Phosphinite-4,5-Dihydrooxazole Ligands 408
42.10.2.1.4.3 Variation 3: Phosphino-4,5-dihydro-1H-imidazole Ligands 408
42.10.2.1.4.4 Variation 4: Phosphinopyridine and Phosphinoquinoline Ligands 408
42.10.2.1.4.5 Variation 5: Pyridylphosphinite and Quinolylphosphinite Ligands 409
42.10.2.1.4.6 Variation 6: Trost Ligands 409
42.10.2.1.5 Method 5: Approaches to Ligands Bearing P-0 and P-N Bonds 410
42.10.2.1.5.1 Variation 1: Phosphinite [P(C,C,O)] Ligands 410
42.10.2.1.5.2 Variation 2: Phosphonite [P(C,O,O)] Ligands 410
42.10.2.1.5.3 Variation 3: Phosphite [P(O,O,O)] Ligands 410
42.10.2.1.5.4 Variation 4: Phosphoramidite [P(O,O,N)] Ligands 410
42.10.2.2 Enantioselective C—C Bond-Forming Reactions 411
42.10.2.2.1 Method 1: Metal-Catalyzed Allylic Alkylation (Tsuji-Trost Reaction) 411
42.10.2.2.1.1 Variations Using 1,3-Symmetrically Substituted Allylic Ligands 411
42.10.2.2.1.2 Variation 2: Using Monosubstituted Allylic Ligands 413
42.10.2.2.1.3 Variation 3: Using 1,3-Dissymmetrically Disubstituted Allylic Substrates ¦¦ 415
42.10.2.2.2 Method 2: Palladium-Catalyzed Arylation of Alkenes (Heck Reaction) ••¦ 418
42.10.2.2.2.1 Variation 1: Selection of Enantiotopic C=C Bonds of an Achiral Substrate • 419
42.10.2.2.2.2 Variation 2: Selection of Enantiotopic Faces of an Achiral Alkenic Substrate 420
42.10.2.2.2.3 Variation 3: Selection of Enantiotopic Sites of an Achiral Alkenic Substrate 423
42.10.2.2.3 Method 3: Metal-Catalyzed Coupling Reactions 424
42.10.2.2.4 Method 4: Conjugate Addition Reactions 427
42.10.2.2.4.1 Variation 1: Metal-Catalyzed 1,4-Addition of Organometallic Reagents to
Activated Alkenes 427
42.10.2.2.4.2 Variation 2: Copper-Catalyzed Asymmetric 1,4-Addition of Organozinc
Reagents 427
42.10.2.2.4.3 Variation 3: Conjugate Addition to Cyclohexa-2,5-dienones 428
42.10.2.2.4.4 Variation 4: Copper-Catalyzed Asymmetric 1,4-Addition of Crignard
Reagents 429
42.10.2.2.4.5 Variation 5: Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboron
Reagents 429
42.10.2.2.5 Methods 5: Miscellaneous Methods 431
42.10.2.2.5.1 Variation 1: Metal-Catalyzed Addition of Organometallic Reagents to
Unactivated Alkenes 431
42.10.2.2.5.2 Variation 2: Metal-Catalyzed Addition of Organometallic Reagents
to Carbonyl Compounds 432
42.10.2.3 Enantioselective C—H Bond-Forming Reactions 433
42.10.2.3.1 Method 1: Rhodium-Promoted Hydrogenation of Alkenes 433
42.10.2.3.2 Method 2: Iridium-Promoted Hydrogenation of Nonfunctionalized
Alkenes 438
42.10.2.3.3 Method 3: Iridium-Promoted Hydrogenation of Imines 441
42.10.2.3.4 Method 4: Ruthenium-Promoted Hydrogenation of Ketones 444
42.10.2.3.5 Method 5: Rhodium-Promoted Hydroformylation of Alkenes 451
42.10.2.3.6 Method 6: Rhodium-Promoted Hydroboration of Alkenes 454
42.ii Applications of Tricoordinated Phosphorus Compounds in
Organocatalysis
J. L. Methot and W. R. Roush
42.11 Applications of Tricoordinated Phosphorus Compounds in
Organocatalysis 469
42.11.1 Method 1: Morita-Baylis-Hillman Reactions 469
42.11.1.1 Variation 1: Tandem Phosphorylsilylation/lreland-Claisen Rearrangement 472
42.11.1.2 Variation 2: Intramolecular Morita-Baylis-Hillman Allylic Alkylation 473
42.11.1.3 Variation 3: ct-Arylation of Enones with Hypervalent Bismuth Reagents • • 474
42.11.1.4 Variation 4: Phosphine-Mediated Reductive Condensation of
Acyloxybutynoates 474
42.11.1.5 Variation 5: Regioselective Allylic Displacement 475
42.11.1.6 Variation 6: The Morita-Baylis-Hillman Reaction Using Air-Stable
Phosphine Reagents 476
42.11.1.7 Variation 7: Asymmetric Morita-Baylis-Hillman Reactions 476
42.11.1.8 Variation 8: The Aza-Morita-Baylis-Hillman Reaction 477
42.11.2 Method 2: Michael Addition Reactions 479
42.11.3 Method 3: Nudeophilic Addition Reactions at Nonactivated Positions • • • 481
42.11.3.1 Variation 1: Chiral Nudeophilic Addition Reactions 484
42.11.3.2 Variation 2: Nudeophilic Interception at the a-Position 485
42.11.3.3 Variation 3: Tandem a- or y-Addition and Michael Addition Reactions — 486
42.11.4 Method 4: [3+2]-Cydoaddition Reactions 487
42.11.5 Method 5: [4+2]-Cydoaddition Reactions 492
42.11.6 Method 6: Acylation and Kinetic Resolution of Alcohols 495
42.11.7 Method 7: Isomerization of Activated Alkynes to Dienes 497
42.12 Product Class 12: Alkylphosphonium Salts
D. Virieux, J.-N. Voile, and J.-L. Pirat
42.12 Product Class 12: Alkylphosphonium Salts 503
42.12.1 Product Subclass 1: Non-Heteroatom-Substituted
Alkylphosphonium Salts 503
42.12.1.1 Synthesis of Product Subclass 1 503
42.12.1.1.1 Methodi: Alkylation of Phosphines 503
42.12.1.1.1.1 Variation 1: Alkylation of Tertiary Phosphines 503
42.12.1.1.1.2 Variation 2: Alkylation of Tertiary Phosphines Using Alcohols or Derivatives 504
42.12.1X1.3 Variation 3: Successive Alkylation of Phosphines, Phosphides, or
Polyphosphines 505
42.12.1.1.1.4 Variation 4: Nucleophilic Addition of Phosphines or Derivatives
to Alkenes or Alkynes 505
42.12.1.1.2 Method 2: Modification of Phosphonium Salts 507
42.12.1.1.2.1 Variation 1: Diels-Alder Reaction of Triphenyl(vinyl)phosphoniurr) Salts
with 1,4-Dienes 507
42.12.1.1.2.2 Variation 2: Modification of Phosphonium Salts by Reaction of Ylides — 507
42.12.1.1.3 Method 3: Reaction of Phosphaalkenes 508
42.12.2 Product Subclass 2: Hydroxyphosphonium Salts 509
42.12.2.1 Synthesis of Product Subclass 2 509
42.12.2.1.1 Method 1: Synthesis of a-Hydroxyphosphonium Salts and Derivatives ¦ ¦ 509
42.12.2.1.1.1 Variation 1: Addition of Phosphines to Aldehydes or Ketones 509
42.12.2.1.1.2 Variation 2: Alkylation of (a-Hydroxyalkyl)phosphines or Derivatives 511
42.12.2.1.1.3 Variation 3: Reaction of Phosphines with Acetals, Ketals, or Hemiacetals • 513
42.12.2.1.1.4 Variation 4: Reaction of Phosphines with Enol Ethers 513
42.12.2.1.2 Method 2: Synthesis of fi-Hydroxyphosphonium Salts and Derivatives • • ¦ 514
42.12.2.1.2.1 Variation 1: Alkylation of Phosphines with (3-Hydroxyalkyl Halides or
Derivatives 514
42.12.2.1.2.2 Variation 2: Alkylation of (P-Hydroxyalkyl)phosphines or Derivatives 517
42.12.2.1.2.3 Variation 3: Reaction of Phosphines with Epoxides 520
42.12.2.1.2.4 Variation 4: Reaction of Ylides with Ketones or Aldehydes 522
42.12.2.1.2.5 Variation 5: Transformation of P-Functionalized Phosphonium Salts 524
42.12.2.1.3 Method 3: Synthesis of y-Hydroxyphosphonium Salts and Derivatives ••• 526
42.12.2.1.3.1 Variation 1: Alkylation of Phosphines with y-Hydroxyalkyl Halides or
Derivatives 526
42.12.2.1.3.2 Variation 2: Alkylation of y-Hydroxyphosphines and Derivatives with
Alky] Halides 528
42.12.2.1.3.3 Variation 3: Reaction of Ylides with Epoxides and 3-Oxaalkyl Halides 529
42.12.2.1.3.4 Variation 4: Transformation of y-Functionalized Phosphonium Salts 530
42.12.3 Product Subclass 3: Sulfanyl- and Selanylphosphonium Salts
and Derivatives 531
42.12.3.1 Synthesis of Product Subclass 3 531
42.12.3.1.1 Method 1: Synthesis of a-Sulfanyl and a-Selanylphosphonium Salts and
Derivatives 531
42.12.3.1.1.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-Substituted
AlkylHalides 531
42.12.3.1.1.2 Variation 2: Alkylation of Phosphines with Bis(sulfanyl)- or Bis(selanyl)
Alkyl Halides, or Cationic Derivatives 533
42.12.3.1.1.3 Variation 3: Transformation of Phosphonium Salts with Anionic Sulfur
Nucleophiles 535
42.12.3.1.1.4 Variation 4: Reaction of Ylides with Sulfur- or Selenium-Containing
Electrophiles 536
42.12.3.1.2 Method 2: Synthesis of P-Sulfanyl- and P-Selanylphosphonium Salts
and Derivatives 537
42.12.3.1.2.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-Containing
AlkylHalidesorSulfonates 538
42.12.3.1.2.2 Variation 2: Reaction of Phosphines with 1,1,2-Trimethyldisulfanium
or 1 -Methyl-1,2-diphenyldisulfanium Salts 539
42.12.3.1.2.3 Variation 3: Reaction of Vinylphosphonium Salts with Sulfur Dioxide,
Thiols, or Associated Anions 540
42.12.3.1.2.4 Variation 4: Reaction of Ylides with Miscellaneous Electrophiles 542
42.12.3.1.3 Method 3: Synthesis of y-Sulfanyl- and y-Selanylphosphonium Salts
and Derivatives 543
42.12.3.1.3.1 Variation 1: Alkylation of Phosphines with Sulfur-or Selenium-Substituted
Alkyl Halides or Related Compounds 543
42.12.3.1.3.2 Variation 2: Transformation of Phosphonium Salts 544
42.12.4 Product Subclass 4: Carbonylphosphonium Salts and Derivatives 545
42.12.4.1 Synthesis of Product Subclass 4 545
42.12.4.1.1 Method 1: Synthesis of P-Carbonylphosphonium Salts and Derivatives •¦ 545
42.12.4.1.1.1 Variation 1: Reaction of Phosphines with Various Carbonyl Electrophiles • ¦ 546
42.12.4.1.1.2 Variation 2: Alkylation of P-Carbonylphosphines with Alkyl Halides or
Sulfonates 548
42.12.4.1.2 Method 2: Synthesis of a-Carbonylphosphonium Salts and Derivatives •¦ 550
42.12.4.1.2.1 Variation 1: Alkylation of Phosphines with a-(Halomethyl)carbonyl Species 550
42.12.4.1.2.2 Variation 2: Reaction of Ylides with Carbonylated Electrophiles 553
42.12.4.1.2.3 Variation 3: Reaction of Stabilized Ylides with Other Electrophiles 556
42.12.4.1.2.4 Variations 4: Miscellaneous Reactions 557
42.12.4.1.3 Method 3: Synthesis of P-Carbonyl-Substituted Phosphonium Salts and
Derivatives 558
42.12.4.U.1 Variation 1: Alkylation of Phosphines with fi-Carbonyl-Substituted Alkyl
Halides 559
42.12.4.1.3.2 Variation 2: Reaction of Phosphines with a,P-Unsaturated Carbonyl
Species 561
42.12.4.1.3.3 Variation 3: Alkylation of p"-Carbonylphosphines with Alkyl Halides 565
42.12.5 Product Subclass 5: Polyphosphonium Salts 565
42.12.5.1 Synthesis of Product Subclass 5 565
42.12.5.1.1 Method 1: Synthesis of Multiphosphonium Salts 566
42.12.5.1.1.1 Variation 1: Reaction with Multihalides 566
42.12.5.1.1.2 Variation 2: Reaction of Unsaturated Precursors 566
42.12.5.1.1.3 Variation 3: Recursive Synthesis from a Phosphine 567
42.12.5.1.2 Method 2: Synthesis of Polymeric Phosphonium Salts 567
42.12.5.1.2.1 Variation 1: Reaction of Phosphonium Monomers 567
42.12.5.1.2.2 Variation 2: Functionalization of Polymeric Backbones 569
42.12.6 Product Subclass 6: Cyclic Phosphonium Salts 570
42.12.6.1 Synthesis of Product Subclass 6 570
42.12.6.1.1 Method 1: Cyclization onto Phosphorus 570
42.12.6.1.1.1 Variation 1: Reaction of Secondary Phosphines or Derivatives with
1,n-Dielectrophiles 570
42.12.6.1.1.2 Variation 2: Intramolecular Cyclization of Tertiary Phosphines 571
42.12.6.1.1.3 Variation 3: Intermolecular Cyclization of Tertiary Phosphines 572
42.12.6.1.1.4 Variation 4: Reaction of Halophosphines 574
42.12.6.1.1.5 Variation 5: Reaction of Methylenephosphonium Ions 575
42.12.6.1.2 Method 2: Cyclization between Two Phosphorus Substituents 576
42.12.7 Product Subclass 7: Heterophosphonium Salts 577
42.12.7.1 Synthesis of Product Subclass 7 577
42.12.7.1.1 Method 1: Synthesis from Tricoordinate Phosphorus Compounds 577
42.12.7.1.1.1 Variation 1: Alkylation of Tricoordinate Reagents 577
42.12.7.1.1.2 Variation 2: Reaction of Phosphines with Heteroatomic Electrophiles — 580
42.12.7.1.2 Method 2: Synthesis from Tetracoordinate Phosphorus Compounds — 581
42.12.7.1.2.1 Variation 1: Modification of Heterophosphonium Salts 581
42.12.7.1.2.2 Variation 2: Reaction of Electrophiles with Tetracoordinate Phosphorus
Derivatives 582
42.12.7.1.2.3 Variation 3: Reaction of Secondary Phosphine-Borane Complexes 582
42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides, Selenides, Tellurides,
and Imides
N. L. Kilah and S. B. Wild
42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides, Selenides, Tellurides,
and Imides 595
42.13.1 Product Subclass 1: Trialkylphosphine Oxides 595
42.13.1.1 Synthesis of Product Subclass 1 595
42.13.1.1.1 Method 1: Oxidation of Trialkylphosphines 595
42.13.1.1.1.1 Variation 1: Oxidation with Hydrogen Peroxide 595
42.13.1.1.1.2 Variation 2: Oxidation with Sulfur(VI) Oxides 596
42.13.1.1.U Variation 3: Oxidation by Nitrous Oxide 597
42.13.1.1.1.4 Variation 4: Oxidation with an lodosylaryl Sulfone 597
42.13.1.1.2 Method 2: Oxidation of Phosphonium Salts 598
42.13.1.1.3 Method 3: Addition of Dialkylphosphine Oxides to Alkenes 599
42.13.1.1.4 Method 4: Addition of Dialkylphosphine Oxides to Ketones or Aldehydes 600
42.13.1.1.5 Method 5: Reactions of Dialkylphosphine Oxides with Alkyl Halides 602
42.13.1.1.5.1 Variation 1: Base-Induced lonization 602
42.13.1.1.5.2 Variation 2: Lewis Acid Catalysis 603
42.13.1.1.5.3 Variation 3: Reduction with Sodium Bis(2-methoxyethoxy)aluminum
Hydride 604
42.13.1.1.6 Method 6: Additions of Dialkyl(chloro)phosphines to Enones 605
42.13.1.1.7 Method 7: Reactions of Chlorophosphine Oxides with Crignard Reagents 606
42.13.1.1.8 Method 8: Reactions of Dialkylphosphinites with Alkyl Halides 607
42.13.1.1.9 Method 9: Isomerization of Dialkylphosphinites 609
42.13.1.1.10 Method 10: Cycloaddition of Alkyl(dichloro)phosphines with Dienes 610
42.13.1.1.11 Method 11: Addition of Dialkylphosphine Oxides to Imines 612
42.13.1.1.12 Method 12: Hydrogenation of Tertiary Arylphosphine Oxides 612
42.13.1.1.13 Method 13: Conversion of Trialkylphosphine Ylides into Trialkylphosphine
Oxides 614
42.13.1.1.14 Method 14: Oxygenation of Trialkylphosphine Imides 615
42.13.1.1.14.1 Variation 1: By Reaction with a Ketone 615
42.13.1.1.14.2 Variation 2: By Reaction with Methanol 615
42.13.1.1.14.3 Variation 3: By Treatment with an Oxidizing Agent 616
42.13.1.1.15 Method 15: Oxygenation of Trialkylphosphine Sulfides 616
42.13.1.1.15.1 Variation 1: Treatment with Phosgene 616
42.13.1.1.15.2 Variation 2: Treatment with Dimethyldioxirane 617
42.13.1.1.15.3 Variation 3: Treatment with Trifluoroacetic Anhydride 617
42.13.1.1.15.4 Variation 4: Treatment with 7-Oxabicyclo[4.1.0]heptane and Trifluoroacetic
Acid 617
42.13.1.1.16 Method 16: Oxygenation of a Trialkylphosphine Selenide 617
42.13.2 Product Subclass 2: Trialkylphosphine Sulfides 618
42.13.2.1 Synthesis of Product Subclass 2 618
42.13.2.1.1 Method 1: Addition of Dialkylphosphine Sulfides to Alkenes 618
42.13.2.1.1.1 Variation 1: Base-Promoted Addition 618
42.13.2.1.1.2 Variation 2: Free-Radical-Initiated Addition 619
42.13.2.1.2 Method 2: Addition of Dialkylphosphine Sulfides to Aldehydes or
Ketones 619
42.13.2.1.3 Method 3: Sulfurization of Trialkylphosphines with Elemental Sulfur — 621
42.13.2.1.4 Method 4: Reaction of Dialkyl(vinyl)phosphine Sulfides with Nucleophiles 621
42.13.2.1.5 Method 5: Reaction of Triethylphosphine with a (Phosphonio)(phos-
phoranylidene)methanethiolate 622
42.13.2.1.6 Method 6: Addition of a 1,3-Diene to an Alkyl(chloro)(methyl-
sulfanyl)phosphine 622
42.13.2.1.7 Method 7: Sulfurization of Trialkylphosphine Oxides 623
42.13.3 Product Subclass 3: Trialkylphosphine Selenides 623
42.13.3.1 Synthesis of Product Subclass 3 623
42.13.3.1.1 Method 1: Addition of a Dialkylphosphine Selenide to an Aldehyde 623
42.13.3.1.2 Method 2: Addition of Potassium Selenocyanate to Trialkylphosphines •• 624
42.13.3.1.3 Method 3: Addition of Elemental Selenium to Trialkylphosphines 625
4Z13.3.1.4 Method 4: Catalytic Reaction of Diphenyl Diselenide and
Tributylphosphine under Microwave Irradiation 625
42.13.3.1.5 Method 5: Reaction of a 1,2,3-Selenadiazole with a Trialkylphosphine ¦¦¦ 626
42.13.4 Product Subclass 4: Trialkylphosphine Tellurides 626
42.13.4.1 Synthesis of Product Subclass 4 626
42.13.4.1.1 Method 1: Addition of Elemental Tellurium to Trialkylphosphines 626
42.13.5 Product Subclass 5: Trialkylphosphine Imides [Trialkyl(imino)phospho-
ranes] 627
42.13.5.1 Synthesis of Product Subclass 5 627
42.13.5.1.1 Method 1: Reaction of an Azide with a Trialkylphosphine
(The Staudinger Reaction) 627
42.13.5.1.2 Method 2: Addition of Base to Aminophosphonium Salts 628
42.13.5.1.3 Method 3: Addition of an lodonium Ylide to Tributylphosphine 628
42.14 Product Class 14: Dialkylphosphinic Acids and Derivatives
J. Drabowicz, J. Lewkowski, C. V. Stevens, D. Krasowska, and R. Karpowicz
42.14 Product Class 14: Dialkylphosphinic Acids and Derivatives 633
42.14.1 Product Subclass 1: Dialkyltrihalophosphoranes and Other
Heteroatom-Containing Analogues 634
42.14.1.1 Synthesis of Product Subclass 1 634
42.14.1.1.1 Methodi: Halogenation of Dialkylhalophosphines 635
42.14.1.1.2 Method 2: Electrochemical Fluorination of Secondary Phosphines 636
42.14.2 Product Subclass 2: Dialkylphosphinic Halides 636
42.14.2.1 Synthesis of Product Subclass 2 636
42.14.2.1.1 Method 1: Halogenation of Tri- and Tetracoordinated Phosphorus-
Containing Precursors 636
42.14.2.1.1.1 Variation 1: Halogenation of Dialkylphosphinic Acids and Derivatives — 636
42.14.2.1.1.2 Variation 2: Halogenation of Dialkylphosphine Oxides 637
42.14.2.1.1.3 Variation 3: Halogenation of Dialkylphosphines and Dialkylphosphinites • 638
42.14.2.1.2 Method 2: Oxidation of Dialkylhalophosphines 638
42.14.2.1.3 Method 3: Synthesis from Dialkyltrihalophosphoranes 639
42.14.3 Product Subclass 3: Dialkylphosphinic Acids 640
42.14.3.1 Synthesis of Product Subclass 3 640
42.14.3.1.1 Methodi: Oxidation of Secondary Dialkylphosphines 640
42.14.3.1.2 Method 2: Dealkylation of Alkyl Dialkylphosphinates 640
42.14.3.1.3 Method 3: Alkylation Reactions of Tri-and Tetracoordinated
Phosphorus-Containing Precursors 641
42.14.3.1.3.1 Variation 1: Alkylation of Hypophosphorous Acid Salts 641
42.14.3.1.3.2 Variation 2: Alkylation of Bis(trimethylsilyl) Phosphonite 642
42.14.3.1.4 Method 4: Hydrolysis of Tetra- and Pentacoordinated Phosphorus-
Containing Precursors 642
42.14.3.1.4.1 Variation 1: Hydrolysis of Dialkylphosphinic Halides 642
42.14.3.1.4.2 Variation 2: Hydrolysis of P,P-Dialkylphosphinic Amides 643
42.14.3.1.4.3 Variation 3: Hydrolysis of Dialkyltrihalophosphoranes 644
42.14.3.1.5 Method 5: Oxidative Cleavage of Tetraalkyldiphosphine Disulfides 644
42.14.3.1.6 Method 6: Reaction of Alkylphosphinic Acids with Alkenes 645
42.14.4 Product Subclass 4: Alkyl/Aryl Dialkylphosphinates 645
42.14.4.1 Synthesis of Product Subclass 4 645
42.14.4.1.1 Methodi: Oxidation of Alkyl/Aryl Dialkylphosphinites 645
42.14.4.1.2 Method 2: Arbuzov Reaction of Dialkyl Alkylphosphonites 646
42.14.4.1.3 Method 3: Reaction of Dialkylphosphinic Halides with Alcohols or Phenols 647
42.14.4.1.4 Method 4: Alkylation of Alkyl Alkylphosphinates 647
42.14.4.1.5 Method 5: Esterification of Dialkylphosphinic Acids and
Transesterification of Alkyl Dialkylphosphinates 649
42.14.5 Product Subclass 5: S-Alkyl/Aryl Dialkylphosphinothioates 650
42.14.5.1 Synthesis of Product Subclass 5 650
42.14.5.1.1 Method 1: S-Alkylation of Dialkylphosphinothioic O-Acids 650
42.14.5.1.2 Method 2: Reaction of Dialkylphosphinic Halides with Thiols 651
42.14.5.1.3 Method 3: Reaction of Secondary Phosphine Oxides or
Dialkylhalophosphine Derivatives with Disulfides or
Thiocarbonyl Derivatives 651
42.14.6 Product Subclass 6: P,P-Dialkylphosphinic Amides 652
42.14.6.1 Synthesis of Product Subclass 6 652
42.14.6.1.1 Method 1: Reaction of Dialkylphosphinic Halides with Amine Derivatives 652
42.14.6.1.2 Method 2: Oxidation of Aminophosphines 653
42.14.6.1.3 Method 3: Reaction of Dialkylhalophosphines with Hydroxylamine
Derivatives 654
42.14.7 Product Subclass 7: Dialkylphosphinothioic Halides 654
42.14.7.1 Synthesis of Product Subclass 7 654
42.14.7.1.1 Method 1: Halogenation of Pentavalent Phosphinothioic Precursors — 654
42.14.7.1.1.1 Variation 1: Halogenation of Dialkylphosphinothioic Acids 654
42.14.7.1.1.2 Variation 2: Halogenation of Tetraalkyldiphosphine Disulfides 655
42.14.7.1.1.3 Variation 3: Halogenation of Se-Alkyl Dialkylphosphinoselenothioates— 655
42.14.7.1.2 Method 2: Addition of Sulfur to Dialkylhalophosphines 656
42.14.7.1.3 Method 3: Reaction of Phosphonothioic Dihalides with Organometallic
Reagents 656
42.14.7.1.4 Method 4: Halogenation of Dialkylphosphinothioic Amides and
S-Amino Derivatives of Dialkylphosphinodithioic Acids 657
42.14.8 Product Subclass 8: Dialkylphosphinothioic O-Acids and Their Sulfur
and Selenium Analogues 658
42.14.8.1 Synthesis of Product Subclass 8 658
42.14.8.1.1 Method 1: Hydrolysis of Dialkylphosphinothioic Halides 658
42.14.8.1.2 Method 2: Preparation of Dialkylphosphinodithioic Acids 658
42.14.8.1.3 Method 3: Preparation of DialkylphosphinoselenothioicSe-Acids 659
42.14.9 Product Subclass 9:0-Alkyl/Ary! Dialkylphosphinothioates 659
42.14.9.1 Synthesis of Product Subclass 9 659
42.14.9.1.1 Method 1: Reaction of Dialkylphosphinothioic Halides with Alcohols
or Phenols 659
42.14.9.1.2 Method 2: Sulfuration of Alkyl Dialkylphosphinites 660
42.14.9.1.3 Method 3: Alkylation of O-Alkyl Alkylphosphinothioates 661
42.14.9.1.4 Method 4: Reaction of Tetraalkyldiphosphine Disulfides or Phosphine
Sulfides 661
42.14.10 Product Subclass 10: Alkyl/Aryl Dialkylphosphinodithioates and
Se-Alkyl/Aryl Dialkylphosphinoselenothioates 662
42.14.10.1 Synthesis of Product Subclass 10 662
42.14.10.1.1 Method 1: Alkylation of Dialkylphosphinodithioic Acids or Their Salts ••• 662
42.14.10.1.2 Method 2: Arbuzov-Type Alkylation of Alkylphosphonotrithioates 662
42.14.10.1.3 Method 3: Reaction of Tetraalkyldiphosphine Disulfides with Disulfides
and Diselenides 663
42.14.11 Product Subclass 11: P.P-Dialkylphosphinothioic Amides 664
42.14.11.1 Synthesis of Product Subclass 11 664
42.14.11.1.1 Method 1: Reaction of Dialkylphosphinothioic Halides with Amines 664
42.14.11.1.2 Method 2: Sulfuration of Aminophosphines 665
42.14.12 Product Subclass 12: Dialkylphosphinoselenoic Halides 665
42.14.12.1 Synthesis of Product Subclass 12 665
42.14.12.1.1 Method 1: Addition of Selenium to Dialkylhalophosphines 665
42.14.13 Product Subclass 13: Dialkylphosphinoselenoic O-Acids and
Dialkylphosphinodiselenoic Acids 666
42.14.13.1 Synthesis of Product Subclass 13 666
42.14.13.1.1 Method 1: Hydrolysis of Dialkylphosphinoselenoic Halides 666
42.14.13.1.2 Method 2: Acidification of Sodium Dialkylphosphinodiselenoates 667
42.14.14 Product Subclass 14: O-Alkyl/Aryl Dialkylphosphinoselenoates 667
42.14.14.1 Synthesis of Product Subclass 14 667
42.14.14.1.1 Method 1: Addition of Selenium to Dialkylphosphinites 667
42.14.14.1.2 Method 2: Reaction of Dialkylphosphinoselenoic Halides with Alcohols • 668
42.14.15 Product Subclass 15: S-Alkyl/Aryl Dialkylphosphinoselenothioates 668
42.14.15.1 Synthesis of Product Subclass 15 668
42.14.15.1.1 Method 1: Addition of Selenium to Dialkylphosphinothioites 668
42.14.16 Product Subclass 16: P,P-Dialkylphosphinoselenoic Amides 669
42.14.16.1 Synthesis of Product Subclass 16 669
42.14.16.1.1 Method 1: Addition of Selenium to Aminophosphines 669
42.14.16.1.2 Method 2: Reaction of Dialkylphosphinoselenoic Halides with Amines ¦• 669
42.14.17 Product Subclass 17: Anhydrides of Dialkylphosphinic Acids and
Their Sulfur and Selenium Analogues 670
42.14.17.1 Synthesis of Product Subclass 17 670
42.14.17.1.1 Method 1: Oxidation of Dialkylphosphine Disulfides 670
42.14.17.1.2 Method 2: Condensation of Dialkylphosphinic Acid Esters with
Dialkylphosphinic Halides and Their Sulfur Analogues 671
42.14.17.1.3 Method 3: Self-Condensation of Dialkylphosphinic Halides and Their
Sulfur Analogues 671
42.14.17.1.4 Method 4: Oxidation or Sulfuration of Dialkylphosphinous Anhydrides • • 673
42.15 Product Class 15: Alkylphosphonic Acids and Derivatives
J. Drabowicz, P. Kietbasinski, P. tyzwa, M. Mikotajczyk, and A. Zajac
42.15 Product Class 15: Alkylphosphonic Acids and Derivatives 679
42.15.1 Product Subclass 1: Alkylphosphonic Dihalides and Their Sulfur and
Selenium Derivatives 680
42.15.1.1 Synthesis of Product Subclass 1 680
42.15.1.1.1 Method 1: Alkylphosphonic Dihalides from Alkylphosphonic Acids
and Their Derivatives 680
42.15.1.1.1.1 Variation 1: Reaction of Phosphonic Acids with Halogenating Reagents •• 680
42.15.1.1.1.2 Variation 2: Reaction of Phosphonic Acid Diesters with Halogenating
Reagents 681
42.15.1.1.2 Method 2: Alkylphosphonic Dihalides from Alkyltetrahalophosphoranes 682
42.15.1.1.3 Method 3: Hydrolytic (or Other) Decompositions of Aluminum Halide
Complexes of Alkyltetrahalophosphoranes 682
42.15.1.1.4 Method 4: Oxidation of Alkyldihalophosphines 683
42.15.1.1.5 Method 5: Alkylphosphonic Dihalides from Phosphorus Trihalides 684
42.15.1.1.5.1 Variation 1: Reaction of Phosphorus Trihalides with Aliphatic Hydrocar¬
bons 684
42.15.1.1.5.2 Variation 2: Other Protocols Based on the Use of Phosphorus Trichloride ¦ 684
42.15.1.1.6 Method 6: Alkylphosphonic Dihalides by Miscellaneous Procedures 684
42.15.1.1.7 Method 7: Synthesis of Alkylphosphonothioic Dihalides 685
42.15.1.1.7.1 Variation 1: Sulfuration of Alkylphosphonic Dihalides 685
42.15.1.1.7.2 Variation 2: Sulfuration of Alkyldihalophosphines 685
42.15.1.1.7.3 Variation 3: Other Protocols 685
42.15.1.1.8 Method 8: Synthesis of Alkylphosphonoselenoic Dihalides 686
42.15.1.1.8.1 Variation 1: Addition of Selenium to Alkyldihalophosphines 686
42.15.2 Product Subclass 2: Alkylphosphonic Adds and Their Sulfur and
Selenium Analogues 686
42.15.2.1 Synthesis of Product Subclass 2 686
42.15.2.1.1 Method 1: Hydrolysis of Alkyltetrachlorophosphoranes 686
42.15.2.1.2 Method 2: Hydrolysis of Alkylphosphonic Dihalides 687
42.15.2.1.3 Method 3: Alkylphosphonic Acids from Alkylphosphonic Acid Esters — 687
42.15.2.1.3.1 Variation 1: Hydrolysis of Alkylphosphonic Acid Esters 687
42.15.2.1.3.2 Variation 2: Dealkylation of Dialkyl Alkylphosphonates 688
42.15.2.1.4 Method 4: Hydrolysis of Alkylphosphonic Acid Amides 689
42.15.2.1.5 Method 5: Disproportionation of Alkylphosphonous Acids 690
42.15.2.1.6 Method 6: In Situ Oxidation of Alkylphosphonous Acids 690
42.15.2.1.7 Method 7: Oxidation of Primary Alkylphosphines 691
42.15.2.1.8 Method 8: Addition of Phosphorous Acid to Alkenes, Carbonyl
Compounds, Imines, and Nitriles 691
42.15.2.1.9 Method 9: Reaction of Phosphorus Trichloride with Carbonyl
Compounds or Carboxylic Acid Derivatives Followed by
Hydrolysis 692
42.15.2.1.10 Method 10: Hydrolysis of 1-Aryl-1-[(4-tolylsulfinyl)amino]methylbis(di-
ethylamino)phosphine-Boranes 693
42.15.2.1.11 Method 11: Synthesis of Alkylphosphonothioic Acids 694
42.15.3 Product Subclass 3: Alkyl/Aryl Alkylphosphonohalidates 694
42.15.3.1 Synthesis of Product Subclass 3 694
42.15.3.1.1 Method 1: Reaction of Dialkyl Alkylphosphonates with Halogenating
Agents 694
42.15.3.1.2 Method 2: Reaction of Aluminum Halide Complexes of
Alkyltetrachlorophosphoranes with Alcohols 695
42.15.3.1.3 Method 3: Reaction of Dialkyl Chlorophosphites with Alkyl Halides 695
42.15.3.1.4 Method 4: Reaction of Alkylphosphonic Dihalides with Alcohols or
Phenols 696
42.15.3.1.5 Method 5: Halogenation of Alkylphosphinates 696
42.15.4 Product Subclass 4: S-Alkyl/Aryl Alkylphosphonohalidothioates and
Sulfur Derivatives 696
42.15.4.1 Synthesis of Product Subclass 4 696
42.15.4.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Thiols 696
42.15.4.1.2 Method 2: Reaction of Alkyldichlorophosphines with Sulfenyl Chlorides • 697
42.15.4.1.3 Method 3: Chlorination of O,O-Dialkyl Alkylphosphonothioates 697
42.15.4.1.4 Method 4: Reaction of Alkylphosphonothioic Dihalides with Alkane-/
Arenethiols 697
42.15.5 Product Subclass 5: P-Alkylphosphonamidic Halides and Their Sulfur
and Selenium Derivatives 698
42.15.5.1 Synthesis of Product Subclass 5 698
42.15.5.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Amines 698
42.15.5.1.2 Method 2: Exchange Reactions of Alkylphosphonic Diamides 699
42.15.5.1.3 Method 3: Rearrangement of Allyl Dialkylphosphoramidochloridites — 699
42.15.5.1.4 Method 4: Oxidative Conversion of Aminochlorophosphines 700
42.15.5.1.5 Method 5: Ring Opening of 1-Functionalized Aziridines with
Alkylphosphonic Dihalides 701
42.15.5.1.6 Method 6: Reaction of Alkylphosphonothioic Dihalides with Amines — 702
42.15.5.1.7 Method 7: Addition of Sulfur to Alkyl(dialkylamino)halophosphines 702
42.15.5.1.8 Method 8: Reaction of Aminesulfenamides with Alkylphosphonic
Dichlorides 703
42.15.5.1.9 Method 9: Reaction of Alkylphosphonoselenoic Dihalides with Amines •¦ 703
42.15.5.1.10 Method 10: Addition of Selenium to Alkyl(chloro)(dialkylamino)phos-
phines 704
42.15.6 Product Subclass 6: Alkyl/Aryl Hydrogen Alkylphosphonates and
Their O-Alkyl/Aryl Sulfur and Selenium Derivatives 704
42.15.6.1 Synthesis of Product Subclass 6 704
42.15.6.1.1 Method 1: Synthesis from Alkylphosphonic Dichlorides 704
42.15.6.1.2 Method 2: Hydrolysis of Alkyl/Aryl Alkylphosphonochloridates 707
42.15.6.1.3 Method 3: Hydrolysis of Diesters of Alkylphosphonic Acids 708
42.15.6.1.4 Method 4: Esterification of Alkylphosphonic Acids 709
42.15.6.1.5 Method 5: Dealkylation of Dialkyl Alkylphosphonates 710
42.15.6.1.5.1 Variation 1: Dealkylation of Dialkyl Phosphonates with Sodium Iodide — 711
42.15.6.1.5.2 Variation 2: Dealkylation of Dialkyl Phosphonates with Sodium Azide — 711
42.15.6.1.5.3 Variation 3: Selective Monodebenzylation of Dibenzyl Phosphonates
with Tertiary Amines 712
42.15.6.1.5.4 Variation 4: Dealkylation of Dialkyl Methylphosphonates with
Diphenylguanidine 713
42.15.6.1.5.5 Variation 5: Silylation-Desilylation Procedure 714
42.15.6.1.6 Method 6: Alkyl/Aryl Hydrogen Alkylphosphonates by Miscellaneous
Methods 714
42.15.6.1.7 Method 7: Hydrolysis of Dialkyl/Diaryl Alkylphosphonothioates 717
42.15.6.1.8 Method 8: Synthesis of O-Alkyl Hydrogen Alkylphosphonothioates
from Alkylphosphonothioic Dichlorides 719
42.15.6.1.9 Method 9: Hydrolysis of O-Alkyl Alkylphosphonochloridothioates 719
42.15.6.1.10 Method 10: Synthesis of O-Alkyl Hydrogen Alkylphosphonothioates
from O-Alkyl Alkylphosphonochloridates 720
42.15.6.1.11 Method 11: Addition of Sulfur to Alkyl Alkylphosphinates 721
42.15.6.1.12 Method 12: Horner-Wadsworth-Emmons Reaction of Phosphonamidates
and Thiophosphonamidates 721
42.15.6.1.13 Method 13: Oxathiaphospholane Approach for the Synthesis of
Nucleoside Methylphosphonothioic Acids 723
42.15.6.1.14 Method 14: Alcoholysis of Monothiophosphonic Anhydrides 724
42.15.6.1.15 Method 15: Synthesis of O-Alkyl Hydrogen Alkylphosphonoselenoat.es ••• 725
42.15.7 Product Subclass 7: S-Alkyl/Aryl Hydrogen Alkylphosphonothioates
and Their Sulfur and Selenium Derivatives 725
42.15.7.1 Synthesis of Product Subclass 7 725
42.15.7.1.1 Method 1: Coupling Reaction of Alkylphosphonic Acids with Thiols 725
42.15.7.1.2 Method 2: Alkylation of Alkylphosphonothioic Acid Anions with Alkyl
Halides 726
42.15.8 Product Subclass 8: P-Alkylphosphonamidic Acids and Their Sulfur
and Selenium Derivatives 726
42.15.8.1 Synthesis of Product Subclass 8 726
42.15.8.1.1 Method 1: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Tertiary
Amines 726
42.15.8.1.2 Method 2: Synthesis of P-Ethylphosphonamidothioic Acids 727
42.15.9 Product Subclass 9: 0,0-Dialkyl/Diaryl Alkylphosphonates and Their
Sulfur and Selenium Derivatives 728
42.15.9.1 Synthesis of Product Subclass 9 728
42.15.9.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Alcohols 728
42.15.9.1.2 Method 2: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Alcohols 728
42.15.9.1.3 Method 3: Reaction of Phosphites with a-Halo Ketones 728
42.15.9.1.4 Method 4: Michaelis-Becker Reaction 728
42.15.9.1.5 Method 5: Michaelis-Arbuzov Reaction 730
42.15.9.1.6 Method 6: Addition of Tricoordinated Organophosphorus Derivatives
to Unsaturated Systems 730
42.15.9.1.6.1 Variation 1: Addition of Dialkyl Phosphites to Alkenes, Allenes, and
Alkynes 730
42.15.9.1.6.2 Variation 2: Addition of Dialkyl Phosphites to Carbonyl Groups 731
42.15.9.1.6.3 Variation 3: Addition of Dialkyl Phosphite Anions to Imines 733
42.15.9.1.7 Method 7: Transesterification Reactions 736
42.15.9.1.8 Method 8: Reaction of Alkyl/Aryl Hydrogen Phosphonates with Alcohols 737
42.15.9.1.9 Method 9: Reaction of O-Alkyl/Aryl Alkylphosphonohalidothioates with
Alcohols 738
42.15.9.1.10 Method 10: Reaction of Alkylphosphonothioic Dihalides with Alcoholates 739
42.15.9.1.11 Method 11: Sulfurization of Tricoordinated Alkylphosphonous Acid
Diesters 740
42.15.9.1.12 Method 12: Miscellaneous Protocols Leading to O,O-Dialkyl/Diaryl
Alkylphosphonothioates 741
42.15.9.1.13 Method 13: Selenation of O,O-Dialkyl/Diaryl Alkylphosphonites 742
42.15.10 Product Subclass 10: O,S-Dialkyl/Oiaryl Alkylphosphonothioates and
Their Sulfur and Selenium Derivatives 743
42.15.10.1 Synthesis of Product Subclass 10 743
42.15.10.1.1 Method 1: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Alkali
Metal Thiolates 743
42.15.10.1.2 Method 2: Reaction of Dithiocarboxylic Acids with Dialkyl Chlorophos-
phites 743
42.15.10.1.3 Method 3: Reaction of Alkyl/Aryl Alkylphosphonohalidodithioates with
Alcohols 743
42.15.10.1.4 Method 4: Reaction of Alkylphosphonic Dihalides with Alcohols and
Thiols, or Sulfanyl Alcohols 743
42.15.10.1.5 Method 5: Alkylation of O-Alkyl/Aryl Alkylphosphonothioate Anions — 745
42.15.10.1.6 Methods 6: Miscellaneous Procedures 746
42.15.11 Product Subclass 11:5,S-Dialkyl/Diaryl Alkylphosphonodithioates
and Their Sulfur and Selenium Derivatives 746
42.15.11.1 Synthesis of Product Subclass 11 746
42.15.11.1.1 Method 1: Arbuzov Reaction of Trialkyl Trithiophosphites with Alkyl
Halides 746
42.15.11.1.2 Method 2: Preparation of Di- and Trithioesters from
Alkylphosphonothioic and Alkylphosphonic Dichlorides 747
42.15.11.1.3 Method 3: Addition of Phosphonodithioyl and Phosphonotrithioyl
Radicals to Alkenes 748
42.15.12 Product Subclass 12:0- and S-Alkyl/Aryl P-Alkylphosphonamidates
and Their Sulfur and Selenium Derivatives 749
42.15.12.1 Synthesis of Product Subclass 12 749
42.15.12.1.1 Method 1: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Amines 749
42.15.12.1.2 Method 2: Reaction of Alkylphosphonic Dichlorides with Amino
Alcohols or with an Alcohol and an Amine 751
42.15.12.1.3 Method 3: Reaction of P-Alkylphosphonamidic Halides with Alcohols ••• 752
42.15.12.1.4 Method 4: Reaction of Dialkyl Amidophosphites with Alkyl Halides 753
42.15.12.1.5 Method 5: Oxidation of Alkylphosphonamidous Acid Esters 754
42.15.12.1.6 Method 6: Aminolysis of Dialkyl Alkylphosphonates 755
42.15.12.1.7 Method 7: Perkov-Type Reaction 755
42.15.12.1.8 Method 8: Reaction of Alkylphosphonothioic Dihalides with Amino
Alcohols 755
42.15.12.1.9 Method 9: Reaction of O-Alkyl/Aryl Alkylphosphonohalidothioates
with Amines 756
42.15.12.1.10 Method 10: Sulfuration or Selenation of Alkylphosphonamidites 757
42.15.13 Product Subclass 13: P-Alkylphosphonic Diamides and Their Sulfur
and Selenium Derivatives 757
42.15.13.1 Synthesis of Product Subclass 13 757
42.15.13.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Amines 757
42.15.13.1.2 Method 2: Reaction of O-Alkyl Phosphorous Diamides with Alkyl Halides 758
42.15.13.1.3 Method 3: Reaction of N,A/,N',A/'-Tetraalkylphosphorodiamidic Chlorides
with Organometallic Reagents 758
42.15.13.1.4 Method 4: Transamination of P-Alkylphosphonic Diamides 759
42.15.13.1.5 Method 5: Oxidation of P-Alkylphosphonous Diamides 759
42.15.13.1.6 Method 6: Sulfurization of Bis(dialkylamino)phosphines 760
42.15.13.1.7 Method 7: Reaction of Alkyl Phosphorodiamidothioites with Alkyl Halides 760
42.15.13.1.8 Method 8: Selenation of Bis(dialkylamino)phosphines 761
42.15.14 Product Subclass 14: Anhydrides of Alkylphosphonic Acids and Their
Derivatives 761
42.15.14.1 Synthesis of Product Subclass 14 761
42.15.14.1.1 Method 1: Reaction of Dialkyl Alkylphosphonates with Halides of
Oxoacids of Phosphorus 761
42.15.14.1.2 Method 2: Reaction of Alkylphosphonic Acids and Their Sulfur
Analogues with Carbodiimides 762
42.15.14.1.2.1 Variation 1: Reaction of Alkylphosphonic Acids with Carbodiimides 762
42.15.14.1.2.2 Variation 2: Reaction of O-Alkyl/Aryl Alkylphosphonothioic Acids with
Carbodiimides 762
42.15.14.1.3 Method 3: Reactions of Alkyl/Aryl Alkylphosphonohalidates and
N.N.P-Trialkylphosphonamidic Halides 763
42.15.14.1.3.1 Variation 1: Reactions of Alkyl/Aryl Alkylphosphonohalidates with
Nucleophiles 763
42.15.14.1.3.2 Variation 2: Reactions of N,N,P-Trialkylphosphonamidic Halides with
Nucleophiles 763
42.15.14.1.4 Method 4: Synthesis of Oligomers of Alkylphosphonic and
Alkylphosphonothioic Anhydrides 764
42.15.14.1.5 Methods 5: Miscellaneous Procedures 766
42.16 Product Class 16: Phosphoric Acid and Derivatives
C. E. McKenna, B. A. Kashemirov, and K. M. Btazewska
42.16 Product Class 16: Phosphoric Acid and Derivatives 779
42.16.1 Product Subclass 1:P=O Phosphates 780
42.16.1.1 Synthesis of Product Subclass 1 780
42.16.1.1.1 Mixed Anhydrides of Phosphoric Acid and Esters of Phosphoric Acid with
Non-Phosphorus-Containing Acids 780
42.16.1.1.1.1 Method 1: Reaction of Phosphates with Anhydrides of Carboxylic Acids • 780
42.16.1.1.1.2 Method 2: Reaction of Phosphate Esters with Anhydrides of Strong
Carboxylic Acids 781
42.16.1.1.1.3 Method 3: Reaction of Phosphates or Phosphate Esters with Amino
Acids in the Presence of Diisopropylcarbodiimide or
Dicyclohexylcarbodiimide 781
42.16.1.1.2 Alkyl Dihydrogen Phosphates 782
42.16.1.1.2.1 Method 1: Phosphorylation of Alcohols with Phosphoryl Chloride 782
42.16.1.1.2.1.1 Variation 1: Phosphorylation of Unprotected Nucleosides 782
42.16.1.1.2.1.2 Variation 2: Phosphorylation of Other Alcohols 783
42.16.1.1.2.2 Method 2: Catalytic Condensation of Phosphoric Acid with Alcohols — 784
42.16.1.1.2.3 Method 3: Phosphoramidites as Phosphorylating Agents 784
42.16.1.1.2.3.1 Variation 1: 5'-Phosphorylation of Solid-Supported Oligonucleotides
by tert-Butyl 2-Cyanoethyl Diisopropylphosphoramidite 785
42.16.1.1.2.3.2 Variation 2: Solid-Phase Phosphoramidites for Selective
Monophosphorylation of Carbohydrates and Nucleosides — 786
42.16.1.1.2.4 Method 4: Disodium 2-((2-[Bis(4-methoxyphenyl)(phenyl)methoxy]eth-
yl}sulfonyl)ethyl Phosphate as a Phosphorylating Agent for
Primary and Secondary Alcohol Functions in Nucleosides — 788
42.16.1.1.3 S-Alkyl Dihydrogen Phosphorothioates 789
42.16.1.1.3.1 Method 1: Selective Dealkylation 789
42.16.1.1.3.2 Method 2: S-Alkylation of Phosphorothioic Acid 790
42.16.1.1.4 Alkyl Trihydrogen Diphosphates 791
42.16.1.1.4.1 Method 1: Phosphorylation byTris(tetrabutylammonium) Hydrogen
Pyrophosphate 791
42.16.1.1.4.1.1 Variation 1: Phosphorylation of Homoallylic 4-Toluenesulfonates or
Allylic Halides 791
42.16.1.1.4.1.2 Variation 2: Phosphorylation of 5'-Tosyl Nucleosides 792
42.16.1.1.4.2 Method 2: Phosphorylation of Activated 5'-Nucleoside Monophosphates 793
42.16.1.1.4.2.1 Variation 1: Activation by Imidazolides 793
42.16.1.1.4.2.2 Variation 2: Activation by Conversion into Phosphorodichloridates 795
42.16.1.1.5 S-Alkyl Trihydrogen Thiodiphosphates 795
42.16.1.1.5.1 Method 1: Thiophosphorylation of 4-Toluenesulfonates or Bromides— 796
42.16.1.1.6 Alkyl Tetrahydrogen Triphosphates 797
42.16.1.1.6.1 Method 1: The Ludwig One-Pot, Three-Step Procedure 797
42.16.1.1.6.2 Method 2: The Ludwig-Eckstein Procedure 798
42.16.1.1.6.3 Method 3: Enzymatic Approaches 799
42.16.1.1.6.4 Method 4: Synthesis via a Reactive Pyrrolidinium Phosphoramidate
Zwitterion Intermediate 801
42.16.1.1.6.5 Method 5: Solid-Phase Synthesis of Nucleoside p-Triphosphates 802
42.16.1.1.7 Anhydrides of Phosphoric Acid: Nucleoside Triphosphate Analogues 804
42.16.1.1.7.1 Method 1: Synthesis of p.y-Methylene Nucleoside Triphosphate
Analogues through Activation by Trihaloacetic Anhydrides
and 1-Methylimidazole 804
42.16.1.1.7.2 Method 2: Synthesis of p.y-Methylene Deoxynucleoside Triphosphate
Analogues via Morpholidates 806
42.16.1.1.7.3 Method 3: Synthesis of a,p-Methylene Deoxynucleoside Triphosphate
Analogues by Enzymatic Phosphorylation of the
Corresponding ct.P-Methylene Deoxynucleoside Diphosphate
Analogues 807
42.16.1.1.8 Alkyl/Aryl Phosphorohalidates 809
42.16.1.1.8.1 Method 1: Phosphorylation with Phosphoryl Chloride 809
42.16.1.1.8.2 Method 2: Synthesis of Alkyl/Aryl Phosphorodifiuoridates 809
42.16.1.1.8.2.1 Variation 1: Fluorination of Alkyl or Aryl Phosphorodichloridates 809
42.16.1.1.8.2.2 Variation 2: Fluorination of P-N Imidazole Derivatives 810
42.16.1.1.9 S-Alkyl/S-Aryl Phosphorodihalidothioates 811
42.16.1.1.10 Dialkyl/Diaryl Hydrogen Phosphates 811
42.16.1.1.10.1 Method 1: Stepwise Esterification of Phosphoryl Chloride 812
42.16.1.1.10.2 Method 2: Selective Hydrolysis of Triesters of Phosphoric Acid 812
42.16.1.1.10.3 Method 3: Solid-Phase Synthesis of Dinucleoside and
Nucleoside-Carbohydrate Phosphodiesters 813
42.16.1.1.11 O,S-Dialkyl/O,5-Diaryl Hydrogen Thiophosphates 814
42.16.1.1.11.1 Method 1: Alkylation of Sulfur in Phosphorothioate Derivatives 815
42.16.1.1.11.2 Method 2: Oxidation of O,S-Disubstituted Phosphonothiolates 816
42.16.1.1.11.3 Method 3: Selective Dealkylation of Triesters Bearing a P—S—C Bond
System 817
42.16.1.1.12 S,S-Dialkyl/S,S-Diaryl Hydrogen Phosphorodithioates 818
42.16.1.1.12.1 Method 1: Reaction of Phosphorodichloridates with Alkane-or
Arenethiols 818
42.16.1.1.12.2 Method 2: Reaction of Elemental Phosphorus with Benzenethiol 818
42.16.1.1.12.3 Method 3: Reaction of /V-(Alkylsulfanyl)phthalimides with Phosphinates
in the Presence of Hexamethyldisilazane 819
42.16.1.1.13 Dialkyl Dihydrogen Diphosphates 820
42.16.1.1.13.1 Method 1: Synthesis of Dialkyl Dihydrogen Diphosphates by
Morpholidate Coupling 820
42.16.1.1.13.2 Method 2: Triphenylphosphine and Di-2-pyridyl Disulfide as Coupling
Agents in One-Pot Syntheses of Symmetrical Dinucleoside
5',5"-Pyrophosphates 821
42.16.1.1.13.3 Method 3: Sugar Nucleoside Diphosphates via a Reactive Zwitterionic
Phosphoramidate Intermediate 822
42.16.1.1.13.4 Method 4: Solid-Phase Synthesis of Symmetrical Nucleoside
Phosphodiesters 823
42.16.1.1.14 Dialkyl/Diaryl Phophorohalidates 825
42.16.1.1.14.1 Method 1: Chlorination of Phosphites with 1,3,5-Trichloro-1,3.5-
triazinane-2,4,6-trione or tert-Butyl(chloro)cyanamide 825
42.16.1.1.14.2 Method 2: Halogenation of Bis(fluoroalkyl) Phosphites 826
42.16.1.1.15 Trialkyl/Triaryl Phosphates 827
42.16.1.1.15.1 Method 1: Addition of Hydrogen Chloride to Vinyl Phosphates 827
42.16.1.1.15.2 Method 2: Phosphorylation 828
42.16.1.1.15.2.1 Variation 1: Phosphorylation with Diphenyl Phosphorochloridate 828
42.16.1.1.15.2.2 Variation 2: Phosphorylation with (2-Oxo-5,5-diphenyloxazolidin-
3-yl)phosphonates 829
42.16.1.1.15.2.3 Variation 3: Phosphorylation Catalyzed by a Low-Molecular-Weight
Peptide-Based Catalyst 832
42.16.1.1.15.3 Method 3: Phosphite Oxidation in the Presence of Alcohols 833
42.16.1.1.15.4 Method 4: Phosphate Esterification Promoted by Silver(l) Oxide 833
42.16.1.1.16 O,O,S-Trialkyl/O,O,S-Triaryl Phosphorothioates 834
42.16.1.1.16.1 Method 1: Synthesis of Phosphorothioates Containing an
a,p-Unsaturated Carbonyl Moiety 834
42.16.1.1.16.2 Method 2: Redox Reaction of a Phosphite with Tellurium Tetrachloride ¦ • 836
42.16.1.1.16.3 Method 3: Solvent-Free S-Alkylation of Phosphites 836
42.16.1.1.17 O,O,Se-Trialkyl/O,O,Se-TriarylPhosphoroselenoates 837
42.16.1.1.17.1 Method 1: Reaction of Potassium O,O-Dialkyl Phosphoroselenoates
with Alkenyl(phenyl)iodonium Salts 837
42.16.1.1.17.2 Method 2: Selenophosphorylation of Silyl Enol Ethers 838
42.16.1.1.18 Tetraalkyl/Tetraaryl Diphosphates 839
42.16.1.1.18.1 Method 1: /V-[Chloro(dimethylamino)methylene]-A/-rnethylmethan-
aminium Chloride as the Condensing Reagent 839
42.16.1.1.18.2 Method 2: Synthesis from a Phosphorochloridate 840
42.16.1.1.19 O,O,0,O-Tetraalkyl/0,O,O,O-Tetraaryl Thiodiphosphates 841
42.16.1.1.19.1 Method 1: Reaction of Phosphites with Sulfur Dichloride 841
42.16.2 Product Subclass 2: P=S Phosphorothioates 842
42.16.2.1 Synthesis of Product Subclass 2 842
42.16.2.1.1 O-Alkyl Dihydrogen Phosphorothioates 842
42.16.2.1.1.1 Method 1: Thiophosphorylation with Thiophosphoryl Chloride 843
42.16.2.1.1.2 Method 2: Sulfurization of Monoalkyl H-Phosphonates 844
42.16.2.1.1.2.1 Variation 1: Sulfurization of Monoalkyl H-Phosphonates with Elemental
Sulfur 844
42.16.2.1.1.2.2 Variation 2: Sulfurization of a Bis(trimethylsilyl) Phosphite Ester 844
42.16.2.1.1.3 Method 3: Sulfurization of Trialkyl Phosphites 845
42.16.2.1.2 O-Alkyl/O-Aryl Dihydrogen Phosphorodithioates 847
42.16.2.1.2.1 Method 1: Oxidation of O-Alkyl Hydrogen Phosphonodithioates 847
42.16.2.1.2.2 Method 2: Sulfurization of Alkyl Phosphonothioates 849
42.16.2.1.2.2.1 Variation 1: Sulfurization of Deoxynucleotide Analogues 849
42.16.2.1.2.2.2 Variation 2: Sulfurization of Peptide Analogues 851
42.16.2.1.2.3 Method 3: Synthesis from Sulfidodithiaphospholanes 853
42.16.2.1.2.3.1 Variation 1: Synthesis of Nucleoside 3'-0-Phosphorodithioates 853
42.16.2.1.2.3.2 Variation 2: Synthesis of Nucleoside 5'-O-Phosphorodithioates 854
42.16.2.1.3 O-Alkyl/O-Aryl Trihydrogen Thiodiphosphates 854
42.16.2.1.3.1 Method 1: Phosphorylation of an O-Alkyl Phosphorothioate 855
42.16.2.1.3.2 Method 2: Synthesis via Imidazolides 855
42.16.2.1.3.3 Method 3: Ring Opening of a 5'-(1 -Thiocyclotriphosphate) with
Ethane-1,2-diamine 856
42.16.2.1.4 O-Alkyl Tetrahydrogen Thiotriphosphates 858
42.16.2.1.4.1 Method 1: Phosphorylation with 2-Chloro-4H-1,3,2-benzodioxaphos-
phinin-4-one and Subsequent Reaction with Pyrophosphate • 858
42.16.2.1.4.2 Method 2: Thiophosphorylation and Subsequent Reaction with
Pyrophosphate 859
42.16.2.1.4.2.1 Variation 1: Direct Thiophosphorylation of the Hydroxy Group 860
42.16.2.1.4.2.2 Variation 2: Thiophosphorylation of Tributylstannyl Ethers 861
42.16.2.1.4.2.3 Variation 3: Enzymatic Phosphorylation 861
42.16.2.1.5 O-Alkyl Tetrahydrogen 1,1-Dithiotriphosphates 862
42.16.2.1.5.1 Method 1: Ring Opening of a 5'-(1 -Sulfidocyclotriphosphate) with
Lithium Sulfide 862
42.16.2.1.5.2 Method 2: Synthesis via 2-Sulfido-1,3,2-Dithiaphospholanes 863
42.16.2.1.6 Anhydrides of Phosphoric Acid: Nucleoside Triphosphate Analogues 865
42.16.2.1.7 O-Alkyl Tetrahydrogen 1,2,3-Trithiotriphosphates 866
42.16.2.1.8 O-Alkyl/O-Aryl Phosphorofluoridothioates 868
42.16.2.1.8.1 Method 1: Sulfurization of Phosphorofluoridites 868
42.16.2.1.8.2 Method 2: Oxidation and Fluorination of Thio-and Dithiophosphonates ¦ 871
42.16.2.1.9 O-Alkyl Phosphorodifluoridothioates 871
42.16.2.1.9.1 Method 1: Sulfurization of a Difluoridophosphite 871
42.16.2.1.9.2 Method 2: Synthesis from a Bis(1H-imidazol-1-yl)phosphinothioate 872
42.16.2.1.10 O,O-Dialkyl/O,O-Diaryl Hydrogen Phosphorothioates 873
42.16.2.1.10.1 Method 1: Stereocontrolled Synthesis via 2-Sulfido-1,3,2-oxathia-
phospholanes 874
42.16.2.1.10.2 Method 2: Stereocontrolled Synthesis via Cyclic N-Acylphosphoramidites 876
42.16.2.1.10.3 Method 3: Stereocontrolled Synthesis via 3'-O-Oxazaphospholidines— 877
42.16.2.1.10.4 Method 4: Sulfurization of Phosphite Triester 880
42.16.2.1.10.4.1 Variation 1: Sulfurization with 3H-1,2-Benzodithiol-3-one 1,1-Dioxide
(Beaucage's Reagent) 880
42.16.2.1.10.4.2 Variation 2: Sulfurization with Phenylacetyl Disulfide 882
42.16.2.1.10.4.3 Variation 3: Sulfurization with 1,V,1",1'"-[Disulfanediylbis(carbono-
thioylnitrilo)]tetraethane 882
42.16.2.1.10.4.4 Variation 4: Sulfurization with Lawesson's Reagent 882
42.16.2.1.10.5 Method 5: Direct Sulfurization of Dialkyl H-Phosphonates 883
42.16.2.1.10.6 Method 6: Polymerization Catalyzed by Uranyl Ion 884
42.16.2.1.11 O,O-Dialkyl/O,O-Diaryl Hydrogen Phosphorodithioates 885
42.16.2.1.11.1 Method 1: Sulfurization of Disubstituted Phosphonodithioates 885
42.16.2.1.11.1.1 Variation 1: From Phosphorochloridites 886
42.16.2.1.11.1.2 Variation 2: Solid-Phase Synthesis of O,O-Dialkyl Phosphorodithoates — 886
42.16.2.1.11.2 Method 2: The Dithiaphospholane Method 888
42.16.2.1.11.2.1 Variation 1: FromN,N-Diisopropyl-1,3,2-dithiaphospholan-2-amine 888
42.16.2.1.11.2.2 Variation 2: From 2-Chloro-1,3,2-dithiaphospholane 890
42.16.2.1.11.3 Method 3: Dithiophosphorylation of Alcohols and Hydrolysis of the
Triester 891
42.16.2.1.11.4 Method 4: Reduction and Subsequent Sulfurization of O.O-Dialkyl
Phosphorochloridothioates 893
42.16.2.1.11.5 Method 5: Solid-Phase Sulfurization of Phosphoramidothioites 893
42.16.2.1.12 O,O-Dialkyl/O,O-Diaryl Phosphorofluoridothioates 895
42.16.2.1.12.1 Method 1: Sulfurization of Phosphorofluoridites 895
42.16.2.1.12.2 Method 2: Fluorination of O,O-Dialkyl Phosphonothioates 896
42.16.2.1.12.3 Method 3: Desulfurization of Phosphorodithioates 897
42.16.2.1.13 O,O,O-Trialkyl/O,O,O-Triaryl Phosphorothioates 898
42.16.2.1.13.1 Method 1: Sulfurization of Trivalent Phosphorus Compounds 898
42.16.2.1.13.1.1 Variation!: Sulfurization with Thiirane 899
42.16.2.1.13.1.2 Variation 2: Sulfurization with Dibenzoyl Tetrasulfide 899
42.16.2.1.13.1.3 Variation 3: Sulfurization with Bis[3-(triethoxysilyl)propyl] Tetrasulfide • • • 899
42.16.2.1.13.2 Method 2: Methanolysis of Phosphoramidothioates 900
42.16.2.1.14 O,O,S-Trialkyl/O,O,S-Triaryl Phosphorodithioates 901
42.16.2.1.14.1 Method 1: Thiophosphorylation of Silyl Enol Ethers 901
42.16.2.1.14.2 Method 2: Alkylation of O,O-Dialkyl Phosphorodithioates 902
42.16.2.1.14.3 Method 3: 5-Alkynylation of Potassium O,O-Dialkyl Phosphorodithioates 902
42.16.2.1.14.4 Method 4: Sulfurization of Phosphorochloridothioates 903
42.16.3 Product Subclass 3: P=Se Phosphates 903
42.16.3.1 Synthesis of Product Subclass 3 904
42.16.3.1.1 O,O-Dialkyl Phosphoroselenoates 904
42.16.3.1.1.1 Method 1: Synthesis via Phosphoramidites 904
42.16.3.1.1.2 Method 2: Synthesis via H-Phosphonates 906
42.16.3.1.1.2.1 Variation 1: Oxidation of O,O-Dialkyl Phosphonates with Potassium
Selenocyanate 906
42.16.3.1.1.2.2 Variation 2: Oxidation of O,O-Dialkyl H-Phosphonates with
Triphenylphosphine Selenide 907
42.16.3.1.1.2.3 Variation 3: Oxidation of O,O-Dialkyl H-Phosphonates with
3H-1,2-Benzothiaselenol-3-one 907
42.16.3.1.1.2.4 Variation 4: Oxidation of O,O-Dialkyl H-Phosphonates with
3-(Phthalimidoselanyl)propanenitrile 909
42.16.3.1.1.3 Method 3: Synthesis via 1,3,2-Oxathiaphospholane 2-Selenides 911
42.16.3.1.2 O,O,O-Trialkyl Phosphoroselenoates 913
42.16.3.1.2.1 Method 1: The Phosphoramidite Approach 913
42.17 Product Class 17: Phosphazenes
S. Urgaonkar and J. C. Verkade
42.17 Product Class 17: Phosphazenes 923
42.17.1 Product Subclass 1: Schwesinger Bases 923
42.17.1.1 Synthesis of Product Subclass 1 924
42.17.1.1.1 Method 1: Synthesis from Phosphonium Salts 924
42.17.1.2 Applications of Product Subclass 1 in Organic Synthesis 925
42.17.1.2.1 Method 1: Deprotonation Reactions 925
42.17.1.2.2 Method 2: Addition of O- and N-Nucleophiles to Alkynes 930
42.17.1.2.3 Method 3: Activation of Arene-Silicon Bonds 930
42.17.1.2.4 Method 4: Halogen-Zinc Exchange Reactions of Aryl Iodides 931
42.17.1.2.5 Method 5: Sigmatropic Rearrangement of Allylic Amines and Alcohols •• 932
42.17.1.2.6 Method 6: Synthesis of Diaryl Ethers and Sulfides 933
42.17.1.2.7 Method 7: Michael Addition 934
42.17.2 Product Subclass 2: Proazaphosphatrane Sulfides 934
42.17.2.1 Synthesis of Product Subclass 2 934
42.17.2.1.1 Method 1: Reaction of Proazaphosphatranes with Sulfur 934
42.17.2.2 Applications of Product Subclass 2 in Organic Synthesis 935
42.17.2.2.1 Method 1: Baylis-Hillman Reaction 935
42.17.3 Product Subclass 3: Proazaphosphatrane Oxides 935
42.17.3.1 Synthesis of Product Subclass 3 936
42.17.3.1.1 Method 1: Reaction of Proazaphosphatranes with Bis(trimethylsilyl)
Peroxide 936
42.17.3.2 Applications of Product Subclass 3 in Organic Synthesis 936
42.17.3.2.1 Methodi: Silylation of Alcohols 936
42.17.3.2.2 Method 2: Transformation of Isocyanates into Carbodiimides 937
42.17.4 Product Subclass 4: Phosphoramides 937
42.17.4.1 Synthesis of Product Subclass 4 938
42.17.4.1.1 Method 1: Synthesis by Oxidation 938
42.17.4.1.2 Method 2: Synthesis by Nudeophilic Substitution 938
42.17.4.2 Applications of Product Subclass 4 in Organic Synthesis 939
42.17.4.2.1 Method 1: Asymmetric Aldol Reactions 939
42.17.4.2.2 Method 2: Enantioselective Allylation Reactions 940
42.17.4.2.3 Method 3: Asymmetric Diels-Alder Reaction 941
42.17.4.2.4 Method 4: Borane Reduction of Ketones 941
42.17.4.2.5 Method 5: Oxidation Reactions 941
42.17.4.2.6 Method 6: Reduction Reactions 942
42.17.4.2.7 Method 7: Conjugate Addition Reactions 943
42.17.5 Product Subclass 5: Linear and Cyclic Organophosphazenes 944
42.17.5.1 Synthesis of Product Subclass 5 944
42.17.5.1.1 Method 1: Reaction of Phosphorus Pentachloride with Ammonium
Chloride or Tris(trimethylsilyl)amine 944
42.17.5.2 Applications of Product Subclass 5 in Organic Synthesis 946
42.17.5.2.1 Method 1: Synthesis of Poly(dichlorophosphazene) 946
42.18 Product Class 18: Pentacoordinated Phosphoranes
T. Kawashima and J. Kobayashi
42.18 Product Class 18: Pentacoordinated Phosphoranes 953
42.18.1 Synthesis of Product Class 18 954
42.18.1.1 Methodic Nudeophilic Substitution on Pentacoordinated Phosphoranes 954
42.18.1.1.1 Variation 1: Addition of Alcohols to Phosphoranes 954
42.18.1.1.2 Variation 2: Addition of Amines to Halophosphoranes 954
42.18.1.1.3 Variation 3: Reaction of Alkoxy-or Aminosilanes with Halophosphoranes ¦ 955
42.18.1.1.4 Variation 4: Reaction of Unsaturated Compounds with Halophosphoranes 955
42.18.1.2 Method 2: Addition to Tetracoordinated Phosphorus Compounds 956
42.18.1.2.1 Variation 1: Addition of Carbonyl Compounds to Phosphorus Ylides 956
42.18.1.2.2 Variation 2: Addition of 1,3-Dipoles to Phosphorus Ylides 958
42.18.1.2.3 Variation 3: Addition to Phosphonium Salts 959
42.18.1.2.4 Variation 4: Addition to Alkylated Iminophosphoranes 962
42.18.1.3 Method 3: Oxidation of Tricoordinated Phosphorus Compounds 963
42.18.1.3.1 Variation 1: Reaction with Dihalogens 963
42.18.1.3.2 Variation 2: Reactions with Other Halogenating Reagents 964
42.18.1.3.3 Variation 3: Reaction with Peroxides 965
42.18.1.3.4 Variation 4: Reaction with a-Diketones 965
42.18.1.3.5 Variation 5: Reaction with a.pMJnsaturated Carbonyl Compounds 967
42.18.1.4 Method 4: Condensation Reactions 968
42.18.1.4.1 Variation 1: Dehydrative Condensation 968
42.18.1.4.2 Variation 2: Reaction of Carbonyl Compounds with Tricoordinated
Phosphorus 970
42.18.1.5 Method 5: Insertion Reactions 971
42.18.1.5.1 Variation 1: Insertion of Tricoordinated Phosphorus 971
42.18.1.5.2 Variation 2: Insertion into the P—H Bond of Hydrophosphoranes 972
42.19 Product Class 19: Hexacoordinated Phosphates
D. Under and J. Lacour
42.19 Product Class 19: Hexacoordinated Phosphates 977
42.19.1 Product Subclass 1: Anionic Hexacoordinated Phosphorus Derivatives
with P-O Bonds Only 978
42.19.1.1 Synthesis of Product Subclass 1 978
42.19.1.1.1 Method 1: Direct Synthesis from Phosphorus Pentachloride 978
42.19.1.1.2 Method 2: Stepwise Synthesis from Phosphorus(lll) Compounds 980
42.19.1.1.2.1 Variation 1: From Phosphites 981
42.19.1.1.2.2 Variation 2: From Phosphorous Triamides 982
42.19.2 Product Subclass 2: Anionic Hexacoordinated Phosphorus Derivatives
with P-0 and P-C Bonds 986
42.19.2.1 Synthesis of Product Subclass 2 986
42.19.2.1.1 Method 1: Stepwise Synthesis from Phosphorus(V) Adducts 986
42.19.2.1.2 Method 2: Direct Oxidation of Phosphoms(lll) Adducts 988
Keyword Index 993
Author Index 1049
Abbreviations 1121 |
| any_adam_object | 1 |
| author_GND | (DE-588)117013870 |
| building | Verbundindex |
| bvnumber | BV035240545 |
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| id | DE-604.BV035240545 |
| illustrated | Illustrated |
| indexdate | 2024-08-20T00:15:11Z |
| institution | BVB |
| isbn | 9783131189516 9781588905338 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-017046349 |
| oclc_num | 634589235 |
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| physical | XLV, 1126 S. graph. Darst. 26 cm |
| publishDate | 2009 |
| publishDateSearch | 2009 |
| publishDateSort | 2009 |
| publisher | Thieme |
| record_format | marc |
| spelling | Science of synthesis Houben-Weyl methods of molecular transformations 42 = Category 5, Compounds with one saturated carbon-heteroatom bond Organophosphorus compounds (incl. RO-P and RN-P) ed. board: D. Bellus ... Stuttgart [u.a.] Thieme 2009 XLV, 1126 S. graph. Darst. 26 cm txt rdacontent n rdamedia nc rdacarrier Bellus, Daniel Sonstige oth Houben, Josef 1875-1940 Sonstige (DE-588)117013870 oth (DE-604)BV013247070 42 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=017046349&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Science of synthesis Houben-Weyl methods of molecular transformations |
| 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_full | Science of synthesis Houben-Weyl methods of molecular transformations 42 = Category 5, Compounds with one saturated carbon-heteroatom bond Organophosphorus compounds (incl. RO-P and RN-P) ed. board: D. Bellus ... |
| title_fullStr | Science of synthesis Houben-Weyl methods of molecular transformations 42 = Category 5, Compounds with one saturated carbon-heteroatom bond Organophosphorus compounds (incl. RO-P and RN-P) ed. board: D. Bellus ... |
| title_full_unstemmed | Science of synthesis Houben-Weyl methods of molecular transformations 42 = Category 5, Compounds with one saturated carbon-heteroatom bond Organophosphorus compounds (incl. RO-P and RN-P) ed. board: D. Bellus ... |
| title_short | Science of synthesis |
| title_sort | science of synthesis houben weyl methods of molecular transformations organophosphorus compounds incl ro p and rn p |
| title_sub | Houben-Weyl methods of molecular transformations |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=017046349&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| volume_link | (DE-604)BV013247070 |
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