Comprehensive enantioselective organocatalysis: catalysts, reactions, and applications
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| 245 | 1 | 0 | |a Comprehensive enantioselective organocatalysis |b catalysts, reactions, and applications |c ed. by Peter I. Dalko |
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CONTENTS
FOREWORD XXVII
PREFACE XXIX
LIST OF CONTRIBUTORS XXXI
ABBREVIATIONS XLI
VOLUME 1: PRIVILEGED CATALYSTS
PART I AMINO ACID-DERIVED CATALYSTS 1
1 PROLINE-RELATED SECONDARY AMINE CATALYSTS AND APPLICATIONS 3
HIYOSHIZO KOTSUKI AND NIIHA SASAKURA
1.1 INTRODUCTION 3
1.2 PROLINAMIDE AND RELATED CATALYSTS 3
1.3 PROLINAMINE AND RELATED CATALYSTS
8
1.4 PROLINE TETRAZOLE AND RELATED CATALYSTS 10
1.5 PROLINAMINE SULFONAMIDE AND RELATED CATALYSTS 13
1.6 PROLINAMINE THIOUREA AND RELATED CATALYSTS 15
1.7 MISCELLANEOUS 16
1.8 CONCLUSIONS 21
ACKNOWLEDGMENTS 21
REFERENCES 21
2 TMS-PROLINOL CATALYST IN ORGANOCATALYSIS 33
HAO JIANG, LUKASZ ALBRECHT, CUSTAV DICKMEISS, KIM L JENSEN, AND
KARL
ANKER
JARGENSEN
2.1 INTRODUCTION 33
2.2 ENAMINE ACTIVATION 34
2.3 IMINIUM-ION ACTIVATION 37
2.4 CASCADE REACTIONS 41
2.5 DIENAMINE ACTIVATION 42
2.6 TRIENAMINE ACTIVATION 46
2.7 SUMMARY AND CONCLUSIONS 48
REFERENCES 48
HTTP://D-NB.INFO/1031647333
VI | CONTENTS
3 NON-PROLINE AMINO ACID CATALYSTS 51
LI-WEN XU AND YIXIN LU
3.1 INTRODUCTION 51
3.2 PRIMARY AMINO ACIDS IN AMINO CATALYSIS 52
3.3 PRIMARY AMINO ACID-DERIVED ORGANIC CATALYSTS 53
3.3.1 UNMODIFIED AMINO ACIDS 55
3.3.2 PROTECTED PRIMARY AMINO ACIDS 55
3.3.3 PRIMARY AMINO ACID-DERIVED DIAMINE CATALYSTS 55
3.3.4 OTHER PRIMARY AMINO ACID CATALYSTS 55
3.4 APPLICATIONS OF NON-PROLINE PRIMARY AMINO ACID CATALYSTS 56
3.4.1 ALDOL REACTION 56
3.4.2 MANNICH REACTION 60
3.4.3 MICHAEL ADDITION 62
3.4.4 OTHER REACTIONS 64
3.5 CONCLUSIONS 65
ACKNOWLEDGMENTS 66
REFERENCES 66
4 CHIRAL IMIDAZOLIDINONE (MACMILLAN'S) CATALYST 69
RAINER MAHRWALD
4.1 INTRODUCTION 69
4.2 ENAMINE CATALYSIS 69
4.3 IMINIUM CATALYSIS 81
4.4 CASCADE REACTION-MERGING IMINIUM AND ENAMINE CATALYSIS 86
REFERENCES 91
5 OLIGOPEPTIDES AS MODULAR ORGANOCATALYTIC SCAFFOLDS 97
ROBERTO FANELLI AND UMBERTO PIARULLI
5.1 INTRODUCTION 97
5.2 C-C BOND FORMING REACTIONS 98
5.2.1 ALDOL REACTIONS 98
5.2.2 MICHAEL REACTIONS 101
5.2.3 MORITA-BAYLIS-HILLMAN REACTIONS 105
5.2.4 HYDROCYANATION OF ALDEHYDES 107
5.3 ASYMMETRIC ACYLATIONS 108
5.4 ASYMMETRIC PHOSPHORYLATIONS 110
5.5 ENANTIOSELECTIVE OXIDATIONS 111
5.6 HYDROLYTIC REACTIONS 114
5.7 SUMMARY AND CONCLUSIONS 114
REFERENCES 114
CONTENTS | VII
PART II NON-AMINO ACID-DERIVED CATALYSTS 117
6 CINCHONAS AND CUPREIDINES 119
STEEN INGEMANN AND HENK HIEMSTRA
6.1 INTRODUCTION 119
6.2 CINCHONA ALKALOID DERIVATIVES 120
6.3 NATURAL CINCHONA ALKALOIDS, CUPREINE, AND CUPREIDINE 121
6.3.1 STRUCTURAL PROPERTIES 121
6.3.2 CATALYSIS WITH NATURAL CINCHONA ALKALOIDS 122
6.3.3 CATALYSIS WITH CUPREINE AND CUPREIDINE 125
6.4 CINCHONA ALKALOIDS WITH AN ETHER OR ESTER GROUP AT C9 127
6.4.1 STRUCTURAL PROPERTIES 127
6.4.2 CATALYSIS WITH C9 ETHERS OF NATURAL CINCHONA ALKALOIDS 127
6.4.3 CATALYSIS WITH C9 ETHERS OF CUPREINE AND CUPREIDINE 129
6.4.4 CATALYSIS WITH C9 ESTERS 133
6.5 CINCHONA ALKALOID DERIVATIVES WITH A SULFONAMIDE, UREA, THIOUREA,
SQUARAMIDE, OR GUANIDINE FUNCTION 134
6.5.1 STRUCTURAL PROPERTIES 134
6.5.2 CATALYSIS WITH C9 AND C6' THIOUREA DERIVATIVES 136
6.5.3 CATALYSIS WITH C9 SULFONAMIDE, SQUARAMIDE, AND GUANIDINE
DERIVATIVES 141
6.6 CINCHONA ALKALOIDS WITH A PRIMARY AMINE GROUP AT C9 145
6.6.1 STRUCTURAL PROPERTIES 145
6.6.2 CATALYSIS WITH C9 AMINO DERIVATIVES 146
6.7 CINCHONA ALKALOIDS IN PHASE-TRANSFER CATALYSIS 149
6.8 ETHER BRIDGED DIMERS 151
6.9 SOME NOVEL CINCHONA ALKALOID DERIVATIVES 153
6.10 PROSPECTS 154
REFERENCES 155
7 CHIRAL C
2
CATALYSTS 161
DAISUKE URAGUCHI, KOHSUKE OHMATSU, AND TAKASHI OOI
7.1 INTRODUCTION 161
7.2 CHIRAL LEWIS BASE CATALYSTS 161
7.2.1 PHOSPHORAMIDES 162
7.2.2 BIPYRIDINE N,N'-DIOXIDES 167
7.2.3 BISPHOSPHINE DIOXIDES 169
7.3 PHOSPHINES 172
7.4 CHIRAL C
2
-SYMMETRIC SECONDARY AND PRIMARY AMINES 174
7.5 CHIRAL C
2
-SYMMETRIC BRENSTED BASES: GUANIDINES 177
7.6 CHIRAL C
2
-SYMMETRIC BRONSTED ACIDS 181
7.6.1 BINAPHTHOL AND BIPHENOL DERIVATIVES 181
7.6.2 PYRIDINIUM DISULFONATES 182
7.6.3 DICARBOXYLIC ACIDS 183
7.6.4 CHIRAL DISULFONIMIDES 186
VIII
| CONTENTS
7.7 CHIRAL C
2
-SYMMETRIC BIS-THIOUREAS 188
7.8 CHIRAL C
2
-SYMMETRIC AMINOPHOSPHONIUM IONS 189
7.9 SUMMARY AND CONCLUSIONS 190
REFERENCES 190
8 PLANAR CHIRAL CATALYSTS 195
OLIVIER R. P. DAVID
8.1 INTRODUCTION 195
8.2 LEWIS/BRANSTED BASES 198
8.2.1 NITROGEN BASES 198
8.2.1.1 AZAFERROCENES 199
8.2.1.2 PYRIDINOFERROCENES 200
8.2.1.3 IMIDAZOLES 204
8.2.1.4 PIP: PARACYCLOPHANE-2,3-DIHYDROIMIDAZOLO[L,2-A]PYRIDINE BASES
204
8.2.1.5 IMINE 205
8.2.2 OXYGEN LEWIS BASES 206
8.2.3 PHOSPHINE 207
8.2.4 N-HETEROCYDIC CARBENES 209
8.2.5 SULFIDES 210
8.3 LEWIS/BRANSTED ACIDS 211
8.3.1 BORONIC ACIDS 211
8.3.2 PHENOLS 212
8.3.3 THIOUREAS 212
8.4 REDOX REACTIONS 213
8.4.1 FLAVIN DERIVATIVES 213
8.4.2 HANTZSCH ESTERS 214
8.5 SUMMARY AND CONCLUSIONS 214
REFERENCES 215
9 DYNAMIC APPROACHES TOWARDS CATALYST DISCOVERY 221
PATRIZIA GALZERANO, CIULIO GASPARINI, MARTA DAL MOLIN, AND
LEONARD J. PRINS
9.1 INTRODUCTION 221
9.2 SELF-ASSEMBLY 222
9.2.1 SELF-ASSEMBLED ORGANOCATALYSTS 223
9.2.2 CATALYSIS IN CONFINED SELF-ASSEMBLED SPACE 227
9.3 SELF-SELECTED CATALYSTS 232
9.3.1 DYNAMIC COMBINATORIAL CHEMISTRY 232
9.4 CONCLUSIONS 236
ACKNOWLEDGMENTS 236
REFERENCES 236
APPENDIX A1
CONTENTS IIX
VOLUME 2: ACTIVATIONS
PART I ASYMMETRIC CATALYSIS WITH NON-COVALENT INTERACTIONS 239
10 BRANSTED ACIDS 241
YUNUS E. TURKMEN, YE ZHU, AND VIRESH H. RAWAL
10.1 INTRODUCTION 241
10.2 CHIRAL ALCOHOL CATALYSTS 245
10.3 CHIRAL SQUARAMIDES AS HYDROGEN-BOND DONOR CATALYSTS 252
10.3.1 INTRODUCTION 252
10.3.1.1 MICHAEL ADDITION REACTION INVOLVING NITROALKENES 253
10.3.1.2 MICHAEL ADDITION REACTION INVOLVING TRCMS-CHALCONES 257
10.3.1.3 MICHAEL ADDITION REACTION INVOLVING OTHER C=C MICHAEL
ACCEPTORS 259
10.3.1.4 REACTIONS INVOLVING A C=N BOND 261
10.3.1.5 REACTIONS INVOLVING A C=0 BOND 261
10.3.1.6 REACTIONS INVOLVING A N=N BOND 263
10.3.1.7 DYNAMIC KINETIC RESOLUTION AND DESYMMETRIZATION 263
10.3.1.8 CASCADE REACTIONS 266
10.3.2 SUMMARY AND OUTLOOK 268
10.4 GUANIDINES/GUANIDINIUMS 269
10.5 MISCELLANEOUS BRANSTED ACIDS 275
10.5.1 AMINOPYRIDINIUMS 275
10.5.2 TETRAAMINOPHOSPHONIUMS 278
10.5.3 AXIALLY CHIRAL DICARBOXYLIC ACIDS 280
10.5.4 STRONGER BRANSTED ACIDS 282
10.6 ADDENDUM 282
REFERENCES 282
11 BRANSTED ACIDS: CHIRAL PHOSPHORIC ACID CATALYSTS IN ASYMMETRIC
SYNTHESIS 289
KEIJI
MORI AND TAKAHIKO AKIYAMA
11.1 INTRODUCTION 289
11.1.1 DESIGN OF CHIRAL PHOSPHORIC ACIDS 289
11.2 REACTION WITH IMINES 291
11.2.1 MANNICH REACTION 291
11.2.2 HYDROPHOSPHONYLATION 293
11.2.3 CYCLOADDITION REACTION 295
11.2.4 TRANSFER HYDROGENATION 297
11.3 FRIEDEL-CRAFTS REACTION 304
11.4 INTRAMOLECULAR ALDOL REACTION 309
11.5 RING OPENING OF MESO-AZIRIDINES 311
11.6 FUTURE PROSPECTS 312
REFERENCES 312
X | CONTENTS
12 BRENSTED ACIDS: CHIRAL (THIO)UREA DERIVATIVES 315
CERGELY JAKAB AND PETER R. SCHREINER
12.1 INTRODUCTION 315
12.1.1 EXPLICIT DOUBLE HYDROGEN-BONDING INTERACTIONS 315
12.1.2 THE BEGINNINGS OF (THIO)UREA CATALYSIS 316
12.2 IMPORTANT CHIRAL (THIO)UREA ORGANOCATALYSTS 318
12.2.1 TAKEMOTO'S CATALYST 318
12.2.2 CINCHONA ALKALOIDS IN (THIO)UREA ORGANOCATALYSIS 322
12.2.3 PYRROLIDINE-(THIO)UREA CATALYSIS 325
12.2.4 NAGASAWA'S CATALYST 326
12.2.5 RICCI'S THIOUREA CATALYST 328
12.2.6 BINAPHTHYLAMINE SCAFFOLDS IN (THIO)UREA CATALYSIS 329
12.2.7 JACOBSEN'S CATALYST FAMILY 330
12.2.8 N-SULFINYL (THIO)UREA CATALYSTS 335
12.3 SUMMARY 336
REFERENCES 336
13 BRENSTED BASES 343
AMAL TING AND SCOTT E. SCHAUS
13.1 INTRODUCTION 343
13.2 CINCHONA ALKALOIDS 344
13.2.1 CINCHONA ALKALOIDS IN ASYMMETRIC TRANSFORMATIONS 345
13.2.2 ASYMMETRIC ACTIVATION OF CONJUGATE ADDITION TO ENONES 346
13.2.3 ASYMMETRIC ACTIVATION OF CONJUGATE ADDITION TO IMINES 347
13.2.4 ASYMMETRIC AMINATIONS 349
13.2.5 ASYMMETRIC ACTIVATION OF ISOCYANOACETATES 350
13.2.6 ASYMMETRIC DIELS-ALDER REACTION 351
13.3 BRENSTED BASE-DERIVED THIOUREA CATALYSTS 352
13.3.1 ASYMMETRIC CONJUGATE ADDITION WITH CARBONYLS AND IMINES 353
13.3.2 ASYMMETRIC CONJUGATE ADDITIONS WITH NON-TRADITIONAL SUBSTRATES
354
13.3.2.1 ASYMMETRIC CASCADE REACTIONS 356
13.4 CHIRAL GUANIDINE CATALYSTS 356
13.4.1 ASYMMETRIC CONJUGATE ADDITION TO ENONES AND IMINES 357
13.4.2 ASYMMETRIC DIELS-ALDER REACTIONS 360
13.5 CONCLUSION 361
REFERENCES 362
14 CHIRAL ONIUM SALTS (PHASE-TRANSFER REACTIONS) 365
SEIJI SHIRAKAWA AND KEIJI
MARUOKA
14.1 INTRODUCTION 365
14.2 PHASE-TRANSFER CATALYSIS 366
14.2.1 PHASE-TRANSFER REACTION OF ACTIVE METHYLENE OR METHINE COMPOUNDS
WITH INORGANIC BASE 366
14.2.1.1 GENERATION OF ONIUM CARBANION 366
14.2.1.2 NUCLEOPHILIC SUBSTITUTION 367
CONTENTS | XI
14.2.1.3 NUDEOPHILIC ADDITION 368
14.2.2 PHASE-TRANSFER CATALYZED ADDITION OF ANION SUPPLIED AS METAL
SALT 370
14.2.3 BASE-FREE NEUTRAL PHASE-TRANSFER REACTION 371
14.3 ONIUM FLUORIDES 372
14.4 ONIUM PHENOXIDES AND RELATED COMPOUNDS 374
14.4.1 ONIUM PHENOXIDES AS LEWIS BASE CATALYSTS 375
14.4.2 ONIUM PHENOXIDES AND RELATED COMPOUNDS AS BRANSTED BASE
CATALYSTS 375
14.5 CONCLUSIONS 377
REFERENCES 377
15 LEWIS BASES 381
PAVEL KOIOVSKY AND ANDREI V. MALKOV
15.1 INTRODUCTION 381
15.2 ALLYLATION REACTIONS 382
15.2.1 CATALYTIC ALLYLATION OF ALDEHYDES 382
15.2.2 STOICHIOMETRIC ALLYLATION OF ALDEHYDES AND KETONES 393
15.3 PROPARGYLATION, ALLENYLATION, AND ADDITION OF ACETYLENES 395
15.3.1 ADDITION TO ALDEHYDES 395
15.3.2 ADDITION TO IMINES 395
15.4 ALDOL-TYPE REACTIONS 396
15.5 CYANATION AND ISONITRILE ADDITION 404
15.5.1 CYANATION OF ALDEHYDES 404
15.5.2 CYANATION OF IMINES (STRECKER REACTION) 407
15.6 REDUCTION REACTIONS 408
15.7 EPOXIDE OPENING 417
15.8 CONCLUSION AND OUTLOOK 421
REFERENCES 421
16 LEWIS ACIDS 431
TATJANA HECKEL AND RENT V/ILHELM
16.1 INTRODUCTION 431
16.2 SILYL CATION BASED CATALYSTS 433
16.3 HYPERVALENT SILICON BASED CATALYSTS 438
16.4 PHOSPHONIUM CATION BASED CATALYSTS 444
16.5 CARBOCATION BASED CATALYSTS 448
16.6 IONIC LIQUIDS 455
16.7 MISCELLANEOUS CATALYSTS 458
16.8 CONCLUSION 459
REFERENCES 459
XIII
CONTENTS
PART II ASYMMETRIC CATALYSIS WITH COVALENT INTERACTIONS 463
17 RATIONALIZING REACTIVITY AND SELECTIVITY IN AMINOCATALYTIC
REACTIONS 465
RAGHAVAN B. SUNOJ
17.1 INTRODUCTION 465
17.2 SECONDARY AMINE CATALYSIS 466
17.2.1 MECHANISM OF SECONDARY AMINE CATALYSIS 466
17.2.1.1 IMPORTANT INTERMEDIATES IN AMINO CATALYSIS 467
17.2.1.2 EXPERIMENTAL IDENTIFICATION OF ENAMINES IN ORGANOCATALYSIS 469
17.2.1.3 ENAMINE RADICAL CATION: THE CONCEPT OF SOMO ACTIVATION 471
17.3 STEREOSELECTIVITY IN PROLINE-CATALYZED REACTIONS 472
17.3.1 TRANSITION STATE MODELS FOR PROLINE-CATALYZED REACTIONS 473
17.3.2 LIMITATIONS OF HYDROGEN-BONDING GUIDED TRANSITION STATE
MODELS 475
17.4 MECHANISM AND STEREOSELECTIVITY IN ORGANOCATALYTIC CASCADE
REACTIONS 482
17.4.1 STEREOSELECTIVITY IN OTHER AMINO ACID CATALYZED REACTIONS 485
17.5 RATIONAL DESIGN OF CATALYSTS 486
17.6 SUMMARY AND CONCLUSIONS 491
ACKNOWLEDGMENTS 492
REFERENCES 492
18 CARBENE CATALYSTS 495
KAREN THAI, EDUARDO SDNCHEZ-LARIOS, AND MICHEL GRAVEL
18.1 INTRODUCTION 495
18.2 REACTIONS OF ACYL ANION EQUIVALENTS 497
18.2.1 BENZOIN REACTION 497
18.2.1.1 HOMO-BENZOIN REACTION 497
18.2.1.2 CROSS-BENZOIN REACTION 498
18.2.1.3 AZA-BENZOIN REACTION 501
18.2.2 STETTER REACTION 501
18.2.2.1 INTRAMOLECULAR STETTER REACTIONS 501
18.2.2.2 INTERMOLECULAR STETTER REACTIONS 503
18.2.2.3 APPLICATION OF STETTER REACTIONS TO NATURAL PRODUCT SYNTHESIS
505
18.2.3 HYDROACYLATION REACTIONS 505
18.3 EXTENDED UMPOLUNG 506
18.3.1 REACTIONS OF A-REDUCIBLE ALDEHYDES 506
18.3.2 REACTIONS OF ENALS AND YNALS 508
18.3.2.1 C-C BOND FORMING REACTIONS AT THE P POSITION 508
18.3.2.2 P-PROTONATION OF HOMOENOLATES 511
18.3.2.3 OXIDATION OF ENALS 513
18.4 UMPOLUNG OF ACTIVATED OLEFINS 514
18.5 NUCLEOPHILIC CATALYSIS 515
18.6 CONCLUSION 518
REFERENCES 518
CONTENTS XIII
19 OXIDES AND EPOXIDES 523
HARRY J. MILNER AND ALAN ARMSTRONG
19.1 ALKENE EPOXIDATION 523
19.1.1 KETONE-MEDIATED EPOXIDATION 524
19.1.2 IMINIUM SALT-CATALYZED EPOXIDATION 532
19.1.3 ASPARTATE-DERIVED PERACID CATALYSIS 536
19.2 HYPERVALENT IODINE-CATALYZED OXIDATIONS 537
19.2.1 ASYMMETRICAL NAPHTHOL DEAROMATIZATION 537
19.2.2 ENANTIOSELECTIVE A-OXYSULFONYLATION OF KETONES 538
19.3 OXIDATION OF THIOETHERS AND DISULFIDES 539
19.4 RESOLUTION OF ALCOHOLS BY OXIDATION 540
REFERENCES 542
20 YLIDES 547
SAIHU LIAO, PENG WANG, AND YONG TANG
20.1 INTRODUCTION 547
20.2 ENANTIOSELECTIVE SULFUR YLIDE CATALYSIS 548
20.2.1 EPOXIDATION 549
20.2.1.1 CATALYSIS VIA SULFIDE ALKYLATION/DEPROTONATION 549
20.2.1.2 CATALYSIS VIA TRANSITION METAL-MEDIATED CARBENE TRANSFER TO
SULFIDES 556
20.2.2 AZIRIDINATION 560
20.2.3 CYDOPROPANATION 562
20.3 ENANTIOSELECTIVE PHOSPHORUS AND ARSENIC YLIDE CATALYSIS 566
20.4 ENANTIOSELECTIVE NITROGEN YLIDE CATALYSIS 570
20.5 ENANTIOSELECTIVE SELENIUM AND TELLURIUM YLIDE CATALYSIS 573
20.6 SUMMARY AND CONCLUSIONS 574
REFERENCES 575
PART III TUNING CATALYST ACTIVITY AND SELECTIVITY BY THE REACTION
MEDIUM AND CONDITIONS 579
21 "NON-CLASSICAL" ACTIVATION OF ORGANOCATALYTIC REACTIONS (PRESSURE,
MICROWAVE IRRADIATION.) 581
PIOTR KWIATKOWSKI, KRZYSZTOF DUDZIHSKI, AND DAWID LYZWA
21.1 INTRODUCTION 581
21.2 ASYMMETRIC ORGANOCATALYSIS UNDER HIGH-PRESSURE CONDITIONS 581
21.3 ASYMMETRIC ORGANOCATALYSIS UNDER MICROWAVE IRRADIATION-THERMAL
EFFECT 593
21.4 ASYMMETRIC ORGANOCATALYSIS UNDER ULTRASOUND IRRADIATION 601
21.5 ASYMMETRIC ORGANOCATALYSIS UNDER BALL MILLING CONDITIONS 605
21.6 SUMMARY AND CONCLUSIONS 612
REFERENCES 613
XIV
| CONTENTS
22 IONIC LIQUID ORGANOCATALYSTS 617
DMITRY E. SIYUTKIN, ALEXANDER S. KUCHERENKO, AND SERGEI G. ZLOTIN
22.1 INTRODUCTION 617
22.2 IONIC LIQUIDS AS RECYCLABLE SOLVENTS FOR ASYMMETRIC ORGANOCATALYTIC
REACTIONS 618
22.2.1 A-AMINO ACID-PROMOTED REACTIONS IN IL MEDIA 618
22.2.2 REACTIONS IN THE PRESENCE OF OTHER CHIRAL ORGANOCATALYSTS IN IL
MEDIA 623
22.3 "NON-SOLVENT" APPLICATIONS OF IONIC LIQUIDS AND THEIR CONGENERS IN
ASYMMETRIC ORGANOCATALYSIS 625
22.3.1 IMMOBILIZATION OF ORGANOCATALYSTS THROUGH ELECTROSTATIC
INTERACTION
WITH IONIC FRAGMENTS 626
22.3.1.1 BIPHASIC NON-COVALENT IMMOBILIZATION ON IONIC LIQUIDS AND
IONIC POLYMERS 626
22.3.1.2 ION-PAIR IMMOBILIZATION ON IONIC LIQUIDS 628
22.3.2 MODIFICATION OF ORGANOCATALYSTS BY IONIC GROUPS THROUGH COVALENT
BONDING 630
22.3.2.1 IONIC ORGANOCATALYSTS INCORPORATING A-AMINO ACID UNITS 631
22.3.2.2 IONIC ORGANOCATALYSTS INCORPORATING A-AMINO AMIDE UNITS 636
22.3.2.3 PYRROLIDINE-SOURCED IONIC ORGANOCATALYSTS 638
22.3.2.4 OTHER ORGANOCATALYSTS BEARING IONIC GROUPS 644
22.4 CONCLUSION 646
REFERENCES 647
23 POLYMER AND MESOPOROUS MATERIAL SUPPORTED ORGANOCATALYSTS 651
TOR ERIK KRISTENSEN AND TORE HANSEN
23.1 INTRODUCTION 651
23.2 POLYMER-SUPPORTED ORGANOCATALYSTS 652
23.2.1 POLYMER RESINS FOR IMMOBILIZATION OF CHIRAL ORGANOCATALYSTS 652
23.2.2 POLYMER-SUPPORTED CINCHONA DERIVATIVES 653
23.2.3 POLYMER-SUPPORTED ENAMINE-IMINIUM ORGANOCATALYSTS 656
23.2.4 MISCELLANEOUS POLYMER-SUPPORTED CHIRAL ORGANOCATALYSTS 662
23.3 MESOPOROUS-SUPPORTED ORGANOCATALYSTS 663
23.3.1 MESOPOROUS MATERIALS FOR IMMOBILIZATION OF CHIRAL
ORGANOCATALYSTS 663
23.3.2 INORGANIC AND INORGANIC-ORGANIC HYBRID MATERIAL SUPPORTED CHIRAL
ORGANOCATALYSTS 664
23.4 CONCLUSIONS AND OUTLOOK 668
REFERENCES 668
24 WATER IN ORGANOCATALYTIC REACTIONS 673
FRANCESCO CIACALONE AND MICHELANGELO CRUTTADAURIA
24.1 INTRODUCTION 673
24.2 ALDOL REACTIONS 678
24.2.1 PRIMARY AMINES 678
CONTENTS I XV
24.2.2 SECONDARY AMINES 682
24.2.3 PROLINES SUBSTITUTED AT THE 4-POSITION 683
24.2.4 PROLINAMIDES 687
24.2.5 SUPPORTED PROLINE AND PROLINE DERIVATIVES 694
24.3 MICHAEL REACTIONS 696
24.4 MANNICH REACTION 705
24.5 DIELS-ALDER REACTION 707
24.6 MISCELLANEOUS EXAMPLES 710
REFERENCES 713
VOLUME 3: REACTIONS AND APPLICATIONS
PART I ALPHA-ALKYLATION AND HETEROATOM FUNCTIONALIZATION 719
25 S
N
2-TYPE ALPHA-ALKYLATION AND ALLYLATION REACTIONS 721
CHRISTINE TRAN AND PETER I. DALKO
25.1 S
N
2-TYPE ALKYLATION UNDER HOMOGENOUS CONDITIONS 721
25.2 DOMINO REACTIONS INCLUDING S
N
2-TYPE ALKYLATIONS 722
25.2.1 MICHAEL/S
N
2 REACTIONS WITH THE HALIDE ON THE DONOR 723
25.2.2 MICHAEL/S
N
2 REACTIONS WITH THE HALIDE ON THE ACCEPTOR 724
25.3 INTERMOLECULAR S
N
2' ALKYLATIONS UNDER HOMOGENOUS
CONDITIONS 726
25.4 SUMMARY 727
REFERENCES 727
26 ALPHA-ALKYLATION BY S
N
1-TYPE REACTIONS 729
ANDREA GUALANDI, DIEGO PETRUZZIELLO, ENRICO EMER, AND PIER GIORGIO COZZI
26.1 INTRODUCTION 729
26.2 S
N
.1-TYPE
NUCLEOPHILIC REACTION BY GENERATION OF CARBOCATIONS 730
26.3 ORGANOCATALYTIC STEREOSELECTIVE S
N
1-TYPE REACTIONS WITH ENAMINE
CATALYSIS 733
26.4 ASYMMETRIC S
N
1-TYPE A-ALKYLATION OF KETONES 737
26.5 COMBINATION OF ENAMINE CATALYSIS AND LEWIS ACIDS IN S
N
.1-TYPE
REACTIONS 738
26.6 ORGANOCATALYTIC S
N
1-TYPE REACTIONS WITH BRANSTED ACIDS 741
26.6.1 ORGANOCATALYTIC S
N
1-TYPE REACTIONS WITH BRANSTED ACIDS AND
METALS 746
26.7 S
N
1-TYPE REACTION PROMOTED BY CHIRAL THIOUREAS 747
26.8 S
N
1-TYPE ORGANOCATALYTIC REACTION OF IMINIUM, OXONIUM, AND
AZIRIDINIUM INTERMEDIATES 749
26.9 CONCLUSIONS AND PERSPECTIVES 751
REFERENCES 751
CONTENTS
27 ALPHA-HETEROATOM FUNATIONALIZATION OF CARBONYL COMPOUNDS 757
GABRIELA CUILLENA
27.1 INTRODUCTION 757
27.2 ENANTIOSELECTIVE A-PNICTOGENATION OF CARBONYL COMPOUNDS 758
27.2.1 AMINATION OF CARBONYL COMPOUNDS 758
27.2.1.1 AZIRIDINATION OF A,(J-UNSATURATED CARBONYL COMPOUNDS 758
27.2.1.2 DIRECT A-AMINATION 761
27.2.2 PHOSPHINATION OF CARBONYL COMPOUNDS 769
27.3 ENANTIOSELECTIVE A-CHALCOGENATION 770
27.3.1 C-0 FORMATION 770
27.3.1.1 DARZENS REACTION 770
27.3.1.2 EPOXIDATION OF A,F}-UNSATURATED CARBONYL COMPOUNDS 771
27.3.1.3 AMINOXYLATION OF CARBONYL COMPOUNDS 774
27.3.1.4 MISCELLANEOUS OXIDATION PROCESSES 777
27.3.2 SULFENYLATION AND SELENENYLATION PROCESSES 778
27.4 ENANTIOSELECTIVE A-HALOGENATION OF CARBONYL COMPOUNDS 779
27.5 SUMMARY AND CONCLUSIONS 783
REFERENCES 783
PART II NUDEOPHILE ADDITION TO C=X BONDS 791
28 ALDOL AND MANNICH-TYPE REACTIONS 793
NOBUYUKI MASE AND CARLOS F. BARBAS III
28.1 INTRODUCTION 793
28.2 ENAMINE CATALYSIS 795
28.2.1 ALDOL REACTIONS IN ENAMINE CATALYSIS 796
28.2.1.1 INTERMOLECULAR ALDOL REACTIONS IN ENAMINE CATALYSIS 796
28.2.1.2 INTRAMOLECULAR ALDOL REACTIONS USING ENAMINE CATALYSIS 799
28.2.1.3 ALDOL REACTIONS IN WATER, ON WATER, AND BY WATER 801
28.2.1.4 METAL-CATALYZED AND ORGANOCATALYTIC REACTION SEQUENCES 805
28.2.1.5 ORGANOCATALYTIC AND BIOCATALYTIC REACTION SEQUENCES 805
28.2.2 MANNICH REACTIONS IN ENAMINE CATALYSIS 806
28.2.2.1 ANTI-SELECTIVE MANNICH REACTIONS 806
28.2.2.2 MANNICH REACTIONS OF ACETALDEHYDE DONORS 809
28.3 BRANSTED ACID CATALYSIS INCLUDING HYDROGEN-BOND CATALYSIS 810
28.3.1 ALDOL REACTIONS IN BRANSTED ACID AND HYDROGEN-BOND CATALYSIS 811
28.3.1.1 INTERMOLECULAR ALDOL REACTIONS IN BRANSTED ACID AND
HYDROGEN-BOND CATALYSIS 811
28.3.1.2 INTRAMOLECULAR ALDOL REACTIONS IN BRANSTED ACID CATALYSIS 814
28.3.2 MANNICH REACTIONS WITH BRANSTED ACID AND HYDROGEN-BOND
CATALYSIS 815
28.3.2.1 VINYLOGOUS MUKAIYAMA MANNICH REACTIONS WITH BRANSTED ACID
CATALYSIS 815
28.3.2.2 MANNICH-TYPE REACTIONS OF ENECARBAMATES WITH BRANSTED ACID
CATALYSIS 816
CONTENTS | XVII
28.3.2.3 MANNICH REACTIONS CATALYZED BY CHIRAL CALCIUM PHOSPHATE 817
28.4 BRONSTED BASE CATALYSIS INCLUDING BIFUNCTIONAL CATALYSIS 817
28.4.1 ALDOL REACTIONS IN BRONSTED BASE CATALYSIS INCLUDING BIFUNCTIONAL
CATALYSIS 818
28.4.1.1 VINYLOGOUS ALDOL REACTIONS IN BRONSTED BASE CATALYSIS 818
28.4.1.2 NITROALDOL (HENRY) REACTIONS WITH BRONSTED BASE CATALYSIS 818
28.4.1.3 BRONSTED BASE CATALYZED ALDOL REACTIONS OF ISATINS 819
28.4.1.4 BRONSTED BASE CATALYZED ALDOL REACTION OF 5 H-OXAZOL-4-ONES 821
28.4.2 MANNICH REACTIONS IN BRONSTED BASE CATALYSIS INCLUDING
BIFUNCTIONAL
CATALYSIS 822
28.4.2.1 SOLVENT-DEPENDENT GUANIDINE BASE CATALYZED MANNICH REACTIONS
822
28.4.2.2 CHIRAL AMMONIUM BETAINE-CATALYZED MANNICH REACTIONS 822
28.4.2.3 QUATERNARY PHOSPHONIUM SALT-CATALYZED MANNICH REACTIONS 823
28.5 PHASE-TRANSFER CATALYSIS 824
28.5.1 ALDOL REACTIONS IN PHASE-TRANSFER CATALYSIS 824
28.5.1.1 AXIALLY CHIRAL QUATERNARY AMMONIUM SALT-CATALYZED ALDOL
REACTIONS 824
28.5.1.2 GUANIDINIUM-THIOUREA-CATALYZED NITROALDOL REACTIONS 825
28.5.2 MANNICH REACTIONS IN PHASE-TRANSFER CATALYSIS 826
28.5.2.1 QUATERNARY AMMONIUM SALT-CATALYZED MANNICH REACTIONS 826
28.5.2.2 GUANIDINIUM-THIOUREA-CATALYZED MANNICH REACTIONS 827
28.5.2.3 QUATERNARY PHOSPHONIUM SALT-CATALYZED MANNICH REACTIONS 828
28.5.3 QUATERNARY AMMONIUM SALT-CATALYZED 6IR ELECTROCYCLIZATION 829
28.6 N-HETEROCYDIC CARBENE (NHC) CATALYSIS 829
28.6.1 NHC-CATALYZED MANNICH-TYPE REACTIONS 829
28.7 SUPPORTED ORGANOCATALYSIS 831
28.7.1 COVALENTLY SUPPORTED ORGANOCATALYSTS 831
28.7.1.1 MAGNETICALLY SUPPORTED ORGANOCATALYSTS 831
28.7.2 NON-COVALENTLY SUPPORTED ORGANOCATALYSTS 832
28.7.2.1 POLYOXOMETALATE-SUPPORTED ORGANOCATALYSTS 832
28.7.2.2 CLAY-SUPPORTED ORGANOCATALYSTS 832
28.7.3 SUPPORTED ORGANOCATALYSTS IN MULTIPHASIC SYSTEMS 834
28.7.3.1 TAGGED ORGANOCATALYSTS 834
28.7.3.2 SUPPORTED IONIC LIQUID PHASE CATALYSIS 834
28.8 SUMMARY AND CONCLUSIONS 835
REFERENCES 835
29 ADDITIONS OF NITROALKYLS AND SULFONES TO C=X 841
AITOR LANCIA, ROSA LDPEZ, MIKE! OIARBIDE, AND CLAUDIO PALOMO
29.1 ORGANOCATALYTIC ADDITION OF NITROALKANES TO C=0 (THE HENRY
REACTION) 841
29.1.1 ORGANOCATALYTIC ADDITION OF NITROALKANES TO ALDEHYDES 841
29.1.2 ORGANOCATALYTIC ADDITION OF NITROALKANES TO KETONES 846
29.2 ADDITION OF NITROALKANES TO C=NR (THE AZA-HENRY OR NITRO-MANNICH
REACTION) 851
XVIII CONTENTS
29.2.1 BRANSTED BASE CATALYZED AZA-HENRY REACTIONS 852
29.2.2 HYDROGEN BOND CATALYZED AZA-HENRY REACTIONS 857
29.2.3 PHASE-TRANSFER CONDITIONS (PTC) 862
29.2.4 MISCELLANEOUS 864
29.3 ORGANOCATALYTIC ADDITION OF SULFONES TO C=X 864
29.3.1 INTRODUCTION 864
29.3.2 ORGANOCATALYTIC ADDITION OF SULFONES TO C=0 864
29.3.3 ORGANOCATALYTIC ADDITION OF SULFONES TO C=N 865
29.4 SUMMARY AND OUTLOOK
868
REFERENCES
868
30 HYDROCYANATION AND STRECKER REACTIONS 873
CARSTEN KRAMER AND STEFAN BRASE
30.1 INTRODUCTION 873
30.1.1 OVERVIEW 873
30.2 AMINO-ACID CONTAINING CATALYSTS FOR CARBONYL HYDROCYANATION 873
30.3 THIOUREA CATALYSTS FOR CARBONYL HYDROCYANATION 875
30.4 C
2
-SYMMETRICAL GUANIDINES AND N,N'-DIOXIDES 876
30.5 DIKETOPIPERAZINES AS CATALYSTS FOR THE STRECKER REACTION 877
30.6 (THIO)UREA CATALYSTS FOR THE STRECKER REACTION 878
30.7 GUANIDINES AS CATALYSTS FOR THE STRECKER REACTION 886
30.8 N,N'-DIOXIDES AND BIS-FORMAMIDES AS CATALYSTS FOR THE STRECKER
REACTION 886
30.9 CHIRAL QUATERNARY AMMONIUM SALTS AS CATALYSTS FOR THE STRECKER
REACTION 890
30.10 BINOL-PHOSPHATES AS CATALYSTS FOR THE STRECKER REACTION 893
30.11 OTHER CATALYSTS FOR THE STRECKER REACTION 895
REFERENCES 896
31 THE MORITA-BAYLIS-HILLMAN (MBH) AND HETERO-MBH REACTIONS 899
YIN WEI AND MIN SHI
31.1 INTRODUCTION 899
31.2 RECENT MECHANISTIC INSIGHTS INTO THE MBH/AZA-MBH REACTION AND
ITS ASYMMETRIC VERSION 900
31.2.1 AMINE CATALYZED MECHANISM 900
31.2.2 PHOSPHINE CATALYZED MECHANISM 905
31.2.3 MECHANISTIC INSIGHTS INTO THE MBH/AZA-MBH REACTION USING
CO-CATALYTIC SYSTEMS OR MULTI-/BIFUNCTIONAL CATALYSTS 906
31.2.4 STEREOSELECTIVITY OF THE MBH/AZA-MBH REACTION 908
31.3 RECENT DEVELOPMENTS OF ESSENTIAL COMPONENTS 910
31.4 RECENT DEVELOPMENTS OF ASYMMETRIC MBH/AZA-MBH
REACTIONS 914
31.4.1 ASYMMETRIC INDUCTION WITH SUBSTRATES 914
31.4.2 CATALYTIC ASYMMETRIC INDUCTION WITH CHIRAL LEWIS BASES 916
31.4.2.1 CHIRAL TERTIARY AMINE CATALYSTS 916
CONTENTS
31.4.2.2 CHIRAL TERTIARY PHOSPHINE CATALYSTS
31.4.3 CATALYTIC ASYMMETRIC INDUCTION WITH
31.4.4 CATALYTIC ASYMMETRIC INDUCTION WITH
31.4.4.1 CATALYTIC ASYMMETRIC INDUCTION WITH
31.4.4.2 CATALYTIC ASYMMETRIC INDUCTION WITH
31.4.4.3 CATALYTIC ASYMMETRIC INDUCTION WITH
31.5 CONCLUSIONS 937
REFERENCES 938
32 REDUCTION OF C=0 AND C=N 941
CUILONG LI AND JON C. ANTILLA
32.1 INTRODUCTION 941
32.2 HANTZSCH ESTER AS THE HYDRIDE SOURCE 941
32.2.1 REDUCTION OF C=N BONDS IN ACYCLIC SYSTEMS 942
32.2.2 REDUCTION OF C=N BONDS IN CYCLIC SUBSTRATES 947
32.2.2.1 REDUCTION OF C=N BONDS IN HETEROARENES 947
32.2.2.2 REDUCTION OF CYCLIC IMINES 948
32.2.3 TRANSFER HYDROGENATION COMBINED WITH OTHER TRANSFORMATIONS 951
32.2.4 IMMOBILIZED CHIRAL CATALYSTS FOR C=N BOND REDUCTION 953
32.2.5 MECHANISTIC CONSIDERATION 954
32.3 TRICHLOROSILANE AS THE REDUCING REAGENT 955
32.3.1 ASYMMETRIC REDUCTION OF KETIMINES 955
32.3.2 REDUCTION OF ENAMINES 960
32.3.3 REDUCTION OF C=N BONDS CATALYZED BY RECOVERABLE LEWIS BASE
CATALYSTS 962
32.3.4 ASYMMETRIC REDUCTION OF C=0 BONDS 963
32.4 OTHER HYDROGEN SOURCES 964
32.4.1 BENZOTHIAZOLINES 964
32.4.2 BORANES 966
32.4.3 HYDROGEN AS THE SOURCE? 967
32.4.3.1 CHIRAL FRUSTRATED LEWIS PAIRS AS CATALYSTS 967
32.4.3.2 H
2
AS A TERMINAL HYDROGEN SOURCE: COMBINED HYDROGENATION BY
ORGANOCATALYSIS AND METAL CATALYSIS 969
32.5 SUMMARY AND CONCLUSIONS 971
REFERENCES 971
PART III NUDEOPHILE ADDITION TO C=C BONDS 975
33 ADDITION TO OT,F)-UNSATURATED ALDEHYDES AND KETONES 977
RAMON RIOS AND XAVIER COMPANYD
33.1 INTRODUCTION 977
33.1.1 IMINIUM ACTIVATION 978
33.1.1.1 HISTORICAL OVERVIEW 978
33.2 NUDEOPHILIC ADDITION TO ENALS AND KETONES 979
33.2.1 IMINIUM ACTIVATION 979
922
CHIRAL LEWIS ACIDS 929
CHIRAL BRANSTED ACIDS 930
CHIRAL THIOUREAS 930
PROLINE DERIVATIVES 933
CHIRAL THIOLS 936
XX | CONTENTS
33.2.1.1 CATALYZED BY SECONDARY AMINES 980
33.2.1.2 PRIMARY AMINE CATALYSIS 982
33.2.1.3 ACDC CATALYSTS 982
33.2.2 SCOPE OF THE NUDEOPHILIC ADDITION TO ENALS 983
33.2.2.1 C-C BOND FORMATION 983
33.2.2.2 C-N BOND FORMATION 989
33.2.2.3 C-O BOND FORMATION 993
33.2.2.4 C-S BOND FORMATION 994
33.2.2.5 C-P BOND FORMATION 994
33.2.2.6 C-H BOND FORMATION 996
33.2.3 SCOPE OF THE NUDEOPHILIC ADDITION TO A,P-UNSATURATED
KETONES 997
33.2.3.1 C-C BOND FORMATION 997
33.2.3.2 C-N BOND FORMATION 1003
33.2.3.3 C-O BOND FORMATION 1004
33.2.3.4 C-S BOND FORMATION 1005
33.2.3.5 OTHER MICHAEL REACTIONS 1006
33.3 CONCLUSION 1008
REFERENCES 1008
34 ADDITION TO NITROOLEFINS AND VINYL SULFONES 1013
CHRISTILE ROUX AND CYRIL BRESSY
34.1 INTRODUCTION 1013
34.2 ADDITION TO NITROOLEFINS 1013
34.2.1 ENAMINE ACTIVATION 1013
34.2.1.1 SECONDARY AMINES 1013
34.2.1.2 PRIMARY AMINES-ANTI-SELECTIVITY 1015
34.2.1.3 APPLICATIONS IN TOTAL SYNTHESIS 1018
34.2.2 HYDROGEN BONDING ACTIVATION 1019
34.2.2.1 CARBON-CENTERED NUCLEOPHILES 1019
34.2.2.2 OXA-MICHAEL ADDITION 1021
34.2.2.3 SULFA-MICHAEL ADDITION 1023
34.2.2.4 AZA-MICHAEL ADDITION 1023
34.2.2.5 APPLICATIONS IN TOTAL SYNTHESIS 1025
34.2.3 ACIDIC ACTIVATION 1026
34.2.4 BASIC ACTIVATION 1026
34.2.5 CHALLENGING SUBSTRATES 1027
34.2.5.1 A,(I-DISUBSTITUTED NITROOLEFINS 1027
34.2.5.2 TERMINALLY UNSUBSTITUTED NITROOLEFINS 1030
34.2.5.3 ACETALDEHYDE 1031
34.2.6 MISCELLANEOUS 1031
34.3 ADDITION TO VINYL SULFONES 1032
34.3.1 ENAMINE ACTIVATION OF ALDEHYDES AND KETONES 1032
34.3.2 NON-COVALENT ACTIVATION 1037
34.4 ADDITION TO VINYL SELENONES 1037
CONTENTS I XXI
34.5 SUMMARY AND CONCLUSIONS 1040
ACKNOWLEDGMENTS 1040
REFERENCES 1040
35 ORGANOCATALYZED ASYMMETRIC ARYLATION AND HETEROARYLATION
REACTIONS 1043
RENATA MARCIA DE FIGUEIREDO AND JEAN-MARC CAMPAGNE
35.1 INTRODUCTION 1043
35.2 REPRESENTATIVE CLASSES OF ELECTROPHILES 1046
35.2.1 A,P-UNSATURATED ALDEHYDES 1046
35.2.2 A,P-UNSATURATED ENONES 1047
35.2.3 NITROOLEFINS 1048
35.2.4 CARBONYL COMPOUNDS 1049
35.2.5 IMINES (AZA-FRIEDEL-CRAFTS REACTION) 1050
35.2.6 OTHER ELECTROPHILES 1051
35.3 FRIEDEL-CRAFTS IN ORGANOCASCADE TRANSFORMATIONS 1053
35.4 APPLICATION IN BIOLOGICALLY INTERESTING AND NATURAL PRODUCT
SYNTHESES 1057
35.5 MISCELLANEOUS 1061
35.6 CONCLUSION 1062
REFERENCES 1063
PART IV RING-FORMING REACTIONS 1067
36 INTRAMOLECULAR REACTIONS 1069
YOU-CAI XIAO AND YING-CHUN CHEN
36.1 INTRODUCTION 3069
36.2 INTRAMOLECULAR RING-FORMING REACTIONS VIA COVALENT CATALYSIS 1070
36.2.1 ENAMINE CATALYSIS 1070
36.2.2 IMINIUM CATALYSIS 1073
36.2.3 SOMO CATALYSIS 1075
36.2.4 CARBENE CATALYSIS 1077
36.2.5 LEWIS BASE CATALYSIS OF TERTIARY AMINES OR PHOSPHINES 1079
36.3 INTRAMOLECULAR RING-FORMING REACTIONS BY NON-COVALENT
CATALYSIS 1081
36.3.1 BRANSTED ACID CATALYSIS 1081
36.3.2 BIFUNCTIONAL CATALYSIS 1085
36.4 CONCLUSION 1087
REFERENCES 1087
37 FORMATION OF 3-, 4- AND 5-MEMBERED CYCLES BY INTERMOLECULAR
REACTIONS 1091
HILINE PELLISSIER
37.1 INTRODUCTION 1091
37.2 ORGANOCATALYTIC ASYMMETRIC SYNTHESIS OF FIVE-MEMBERED CYCLES 1092
XXII | CONTENTS
37.2.1 SYNTHESIS OF FIVE-MEMBERED CYCLES VIA [3+2] CYDOADDITIONS 1092
37.2.1.1 [3+2] CYDOADDITIONS OF NITRONES 1092
37.2.1.2 [3+2] CYDOADDITIONS OF AZOMETHINE YLIDES 1096
37.2.1.3 MISCELLANEOUS [3+2] CYDOADDITIONS 1098
37.2.2 FIVE-MEMBERED CYCLES VIA DOMINO REACTIONS 1101
37.2.2.1 DOMINO REACTIONS INITIATED BY THE MICHAEL REACTION 1101
37.2.2.2 MISCELLANEOUS DOMINO REACTIONS 1110
37.3 ORGANOCATALYTIC ASYMMETRIC SYNTHESIS OF FOUR-MEMBERED
CYCLES 1112
37.4 ORGANOCATALYTIC ASYMMETRIC SYNTHESIS OF THREE-MEMBERED
CYCLES 1115
37.4.1 SYNTHESIS OF CYCLOPROPANES 1115
37.4.2 SYNTHESIS OF AZIRIDINES 1120
37.5 CONCLUSION 1123
REFERENCES 1124
38 DIELS-ALDER AND HETERO-DIELS-ALDER REACTIONS 1131
HAIFENG DU AND KUILING DING
38.1 INTRODUCTION 1131
38.2 ORGANOCATALYTIC DIELS-ALDER REACTION 1132
38.2.1 CHIRAL SECONDARY OR PRIMARY AMINES AS CATALYSTS 1132
38.2.1.1 CHIRAL SECONDARY AMINE 1132
38.2.1.2 CHIRAL PRIMARY AMINE 1140
38.2.2 CHIRAL BRANSTED ACIDS CATALYSTS (HYDROGEN-BONDING OR BRANSTED
ACID
ACTIVATION) 1142
38.2.3 CHIRAL BIFUNCTIONAL CATALYSTS 1144
38.3 ORGANOCATALYSIS OF OXA-HETERO-DIELS-ALDER REACTION 1147
38.3.1 CHIRAL BASES AS CATALYSTS 1148
38.3.2 CHIRAL BRANSTED ACIDS AS CATALYSTS 1150
38.3.3 CHIRAL N-HETEROCYDIC CARBENES AS CATALYSTS 1152
38.4 ORGANOCATALYSIS OF AZA-HETERO-DIELS-ALDER REACTION 1154
38.4.1 CHIRAL CARBENES AS CATALYSTS 1154
38.4.2 CHIRAL AMINES AS CATALYSTS 1155
38.4.3 CHIRAL BRANSTED ACIDS AS CATALYSTS 1157
38.5 CONCLUSION 1159
REFERENCES 1160
PART V INCREASING COMPLEXITY 1163
39 ORGANOCATALYTIC RADICAL AND ELECTRON TRANSFER REACTIONS 1165
THIBAULT CALLAVARDIN AND PETER I. DALKO
39.1 INTRODUCTION 1165
39.2 CHEMICALLY INDUCED OXIDATIVE ELECTRON-TRANSFER REACTIONS
1166
39.2.1 OXAMINATION REACTIONS 1169
39.2.2 ADDITIONS TO OLEFINS AND ALKYNES 1169
CONTENTS XXIII
39.2.3 ASYMMETRIC INTERMOLECULAR ALLYLATION OF ALDEHYDES 1170
39.2.4 ASYMMETRIC ALLYLATION OF KETONES 1172
39.2.5 INTRAMOLECULAR ASYMMETRIC ALLYLATIONS 1172
39.2.6 A-ENOLATION 1173
39.2.7 A-VINYLATION 1174
39.2.8 CARBO-OXIDATION OF STYRENES 1175
39.2.9 POLYENE CYDIZATIONS 1175
39.2.10 INTRAMOLECULAR A-ARYLATION 1176
39.2.11 CASCADE CYDOADDITIONS 1177
39.2.12 ASYMMETRIC NITROALKYLATION OF ALDEHYDES 1180
39.3 PHOTOREDOX CATALYSIS 1180
39.3.1 A-ALKYLATION OF ALDEHYDES 1182
39.3.2 A-BENZYLATION OF ALDEHYDES 1184
39.3.3 A-TRIFLUOROMETHYLATION OF ALDEHYDES 1185
39.4 PHOTOCHEMICAL ASYMMETRIC SYNTHESIS 1186
39.5 CONCLUSION 1188
REFERENCES 1189
40 ORGANOCATALYTIC SIGMATROPIC REACTIONS 1191
CUILLEM VALERO AND ALBERT MOYANO
40.1 INTRODUCTION 1191
40.2 STEGLICH AND RELATED REARRANGEMENTS 1192
40.3 1,3-SIGMATROPIC REARRANGEMENTS 1203
40.4 1,4-SIGMATROPIC REARRANGEMENTS 1207
40.5 2,3-SIGMATROPIC REARRANGEMENTS 1208
40.6 3,3-SIGMATROPIC REARRANGEMENTS 1209
40.7 AZA-PETASIS-FERRIER REARRANGEMENT 1215
40.8 PINACOL AND RELATED REARRANGEMENTS 1216
ACKNOWLEDGMENTS 1220
REFERENCES 1220
41 REGIO- AND POSITION SELECTIVE REACTIONS AND DESYMMETRIZATIONS 1225
ALAN C. SPIVEY AND STELLIOS ARSENIYADIS
41.1 INTRODUCTION 1225
41.2 KINETIC RESOLUTION OF ALCOHOLS 1225
41.2.1 ACYLATION-BASED PROCESSES 1225
41.2.1.1 MECHANISTIC STUDIES 1226
41.2.1.2 SYNTHETIC STUDIES 1229
41.2.2 PHOSPHORYLATION-BASED PROCESS 1251
41.2.3 SULFONYLATION- AND SULFINYLATION-BASED PROCESS 1256
41.2.4 SILYLATION-BASED PROCESS 1258
41.3 KINETIC RESOLUTION OF AMINES 1263
41.3.1 ACYLATION-BASED PROCESS 1263
41.4 CONCLUDING REMARKS 1278
REFERENCES 1279
XXIV
| CONTENTS
42 THREE OR MORE COMPONENTS REACTIONS (SINGLE CATALYST SYSTEMS) 1285
RENT TANNERT, ANTONIO MORAN, AND PAOLO MELCHIORRE
42.1 GENERAL INTRODUCTION 1285
42.2 COVALENT MODES OF CATALYSIS-DEVELOPING MCRS BY ASYMMETRIC
AMINOCATALYSIS 1287
42.2.1 ASYMMETRIC MCRS BASED ON A SINGLE AMINOCATALYTIC STEP 1288
42.2.2 ASYMMETRIC MCRS BASED ON TWO AMINOCATALYTIC STEPS 1294
42.2.3 ASYMMETRIC MCRS BASED ON THREE OR MORE AMINOCATALYTIC
STEPS 1300
42.2.4 ONE-POT ASYMMETRIC MCRS FOR THE PREPARATION OF ACTIVE
PHARMACEUTICAL INGREDIENTS 1307
42.3 NON-COVALENT MODES OF CATALYSIS 1309
42.3.1 INTRODUCTION 1309
42.3.2 MANNICH REACTIONS 1310
42.3.3 STRECKER REACTIONS 1314
42.3.4 KABACHNIK-FIELDS REACTION 1314
42.3.5 PETASIS REACTION 1315
42.3.6 UGI-TYPE REACTION 1317
42.3.7 REDUCTIVE ANIMATION 1317
42.3.8 HANTZSCH DIHYDROPYRIDINE AND RELATED REACTIONS 1319
42.3.9 BIGINELLI REACTIONS 1321
42.3.10 1,3-DIPOLAR (HUISGEN) CYCLOADDITION REACTIONS 1322
42.3.11 DIELS-ALDER REACTIONS 1324
42.3.12 OTHER REACTIONS 1325
42.4 MERGING COVALENT AND NON-COVALENT ACTIVATION MODES 1325
42.5 SUMMARY AND OUTLOOK 1326
ACKNOWLEDGMENTS 1327
REFERENCES 1327
43 MULTI-CATALYST SYSTEMS 1333
LIU/EN
XU, HUAMENG YANG, AND ZHIHUI SHAO
43.1 INTRODUCTION 1333
43.2 COMBINATIONAL USE OF DUAL BRANSTED ACIDS 1334
43.3 COMBINATIONAL USE OF CHIRAL BRONSTED ACID AND CHIRAL OR ACHIRAL
LEWIS BASE 1335
43.4 CARBENE-BASED DUAL ORGANOCATALYSIS 1338
43.5 AMINO CATALYST-BASED COOPERATIVE CATALYSIS WITH MULTIFARIOUS
CO-CATALYSTS 1343
43.6 CONCLUSIONS 1354
ACKNOWLEDGMENTS 1355
REFERENCES 1355
CONTENTS | XXV
44 ORGANOCATALYSIS IN TOTAL SYNTHESIS 1359
EUGENIA MARQUIS-LDPEZ AND RAQUEL P. HERRERA
44.1 INTRODUCTION 1359
44.2 AMINOCATALYSIS IN NATURAL PRODUCT SYNTHESIS 1359
44.2.1 ENAMINE CATALYSIS 1360
44.2.2 DIENAMINE CATALYSIS 1363
44.2.3 IMINIUM CATALYSIS 1363
44.2.4 ORGANOCASCADE CATALYSIS: COMBINATIONS OF ENAMINE AND IMINIUM
CATALYSIS 1365
44.3 HYDROGEN BOND CATALYSIS IN TOTAL SYNTHESIS 1365
44.3.1 PHOSPHORIC ACIDS 1366
44.3.2 (THIO)UREA ORGANOCATALYZED PROCESSES 1368
44.4 CINCHONA ALKALOIDS IN TOTAL SYNTHESIS 1370
44.5 PHASE-TRANSFER CATALYSIS IN TARGET MOLECULE SYNTHESIS 1371
44.6 INDUSTRIAL APPLICATIONS OF ORGANOCATALYSIS 1373
44.6.1 AMINOCATALYSIS IN THE INDUSTRIAL SECTOR 1373
44.6.2 THIOUREA CATALYSIS AT THE INDUSTRIAL SCALE 1374
44.6.3 CINCHONA ALKALOIDS AT THE INDUSTRIAL LEVEL 1375
44.6.4 PHASE-TRANSFER CATALYSIS IN INDUSTRY 1376
44.7 CONCLUSIONS 1376
REFERENCES 1377
INDEX 1385 |
| any_adam_object | 1 |
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| building | Verbundindex |
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| discipline | Chemie / Pharmazie |
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| id | DE-604.BV041293600 |
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| indexdate | 2024-08-03T00:57:38Z |
| institution | BVB |
| isbn | 9783527332366 9783527658862 |
| language | English |
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| spelling | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications ed. by Peter I. Dalko Weinheim Wiley-VCH txt rdacontent n rdamedia nc rdacarrier Organokatalyse (DE-588)7636906-7 gnd rswk-swf Asymmetrische Synthese (DE-588)4135603-2 gnd rswk-swf (DE-588)4143413-4 Aufsatzsammlung gnd-content Organokatalyse (DE-588)7636906-7 s Asymmetrische Synthese (DE-588)4135603-2 s DE-604 Dalko, Peter I. 1960- Sonstige (DE-588)132717719 oth Erscheint auch als Online-Ausgabe, EPUB 978-3-527-65888-6 Erscheint auch als Online-Ausgabe, MOBI 978-3-527-65887-9 Erscheint auch als Online-Ausgabe, PDF 978-3-527-65889-3 X:MVB text/html http://deposit.dnb.de/cgi-bin/dokserv?id=4260003&prov=M&dok_var=1&dok_ext=htm Inhaltstext DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=026742535&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications Organokatalyse (DE-588)7636906-7 gnd Asymmetrische Synthese (DE-588)4135603-2 gnd |
| subject_GND | (DE-588)7636906-7 (DE-588)4135603-2 (DE-588)4143413-4 |
| title | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications |
| title_auth | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications |
| title_exact_search | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications |
| title_full | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications ed. by Peter I. Dalko |
| title_fullStr | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications ed. by Peter I. Dalko |
| title_full_unstemmed | Comprehensive enantioselective organocatalysis catalysts, reactions, and applications ed. by Peter I. Dalko |
| title_short | Comprehensive enantioselective organocatalysis |
| title_sort | comprehensive enantioselective organocatalysis catalysts reactions and applications |
| title_sub | catalysts, reactions, and applications |
| topic | Organokatalyse (DE-588)7636906-7 gnd Asymmetrische Synthese (DE-588)4135603-2 gnd |
| topic_facet | Organokatalyse Asymmetrische Synthese Aufsatzsammlung |
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