Roos Key Chiral Auxiliary Applications

2. Auflage 2014
ISBN: 978-0-12-417115-2
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 1270 Seiten

Key Chiral Auxiliary Applications, Second Edition is a detailed compilation of chiral auxiliary applications organized by type of transformation. Continuing from the most important and relevant auxiliaries described in its predecessor, the three-volume set Compendium of Chiral Auxiliary Applications (2001), as well as advances in the field, the book provides a vital and timely resource for chemists in the field. Each reaction class includes a series of tables and graphical abstracts of real reactions from the literature and patents to enable easy review and comparison of results. This anticipated edition is based on a screening of nearly 40,000 auxiliary reaction applications, with details supplied for the more than 13,000 selected representative entries: synthetic route, reagents, yields, diastereomeric/enantiomeric excesses, and characterization data. Updated and streamlined with more than 60% new material, Key Chiral Auxiliary Applications provides valuable guidance and reliable content for selecting the best auxiliary for a specific asymmetric synthetic transformation. - Provides a comprehensive compilation based on nearly 40,000 diverse applications of chiral auxiliaries for selecting the best synthetic route to optically pure compounds - Contains over 60% new material with 13,000+ auxiliary applications categorized by reaction type, with reaction details and chemical and optical yields in one unique resource

Greg Roos' formal education comprised of a BSc (1971), BSc Honours (1972), and PhD in Organic Synthesis (1976) from the University of Cape Town. A postdoctoral fellowship with Richard Cookson at the University of Southampton was followed by a few years of pharmaceutical industrial experience. His fulltime academic career involved the University of Natal, South Africa (1981-1994), Murdoch University, Australia (1994-1997), and an extended period in the Middle East, including Sultan Qaboos University, Oman (1998-2004) and The Petroleum Institute, Abu Dhabi (2004-2008). He has successfully taught across various cultures and has received awards for his teaching contributions and innovations. Since 2009, as an adjunct Professor at Murdoch University, he shares his time between Australia and Dubai.His research interests have focused on the development of synthetic methodology, with particular interest in asymmetric processes. This provided numerous publications in the areas of the Baylis-Hillman reaction, imidazolidinone chiral auxiliaries, and dirhodium catalyst development and applications. This period also included a number of productive collaborative visits with Tony McKervey (University College Cork & Queen's University, Belfast), C. K. Sha (Shin Hua University, Taiwan), Mike Doyle (Trinity University, San Antonio), and Ron Warrener (CQU Rockhampton, Queensland). In 2001 he received the Merck Gold Medal for research from the South African Chemical Institute.

Autoren/Hrsg.

Roos, Gregory

Inhaltsverzeichnis

1;Front Cover;1
2;Key Chiral Auxiliary Applications;4
3;Copyright;5
4;CONTENTS;6
5;ACKNOWLEDGEMENTS;20
6;FOREWORD;22
7;PREFACE TO THE 2ND EDITION;24
8;ABBREVIATIONS;26
9;1.
INTRODUCTION;28
9.1;1.1. BACKGROUND;28
9.2;1.2. THE CHIRAL AUXILIARY APPROACH;29
9.3;1.3. THIS COLLECTION;30
9.4;REFERENCES;32
10;2.
ALKYLATION AND RELATED REACTIONS I;36
10.1;2.1 ALLYL AND BENZYL RELATED CARBANIONS;37
10.2;2.2 ALLENIC ETHER TANDEM ACYLATION-CYCLIZATION;51
10.3;2.3 ALDEHYDE DERIVED NUCLEOPHILES;53
10.4;2.4 KETONE DERIVED NUCLEOPHILES;63
10.5;2.5 ALDEHYDE AND KETONE ENOLATES WITH AUXILIARY-CONTAINING ELECTROPHILES;88
10.6;REFERENCES;91
11;3.
ALKYLATION AND RELATED REACTIONS II;96
11.1;3.1 a-ALKYLATION OF CARBOXYLIC ACID DERIVED NUCLEOPHILES;98
11.2;REFERENCES;191
12;4.
ALKYLATION AND RELATED REACTIONS III;200
12.1;4.1 a-ALKYLATION OF -HETEROATOM SUBSTITUTED ACID DERIVATIVES;201
12.2;4.2 a-ALKYLATION OF CYCLIC CARBOXYLIC ACID DERIVATIVES;272
12.3;REFERENCES;282
13;5.
ALKYLATION AND RELATED REACTIONS IV;290
13.1;5.1 a-ACYLATION OF ACID DERIVATIVES;291
13.2;5.2 a-AMINATION OF ACYL DERIVATIVES;312
13.3;5.3 a-HYDROXYLATION OF ACID DERIVATIVES;290
13.4;5.4 a-SILYLATION, a-THIOLATION, AND a-SELENATION OF ACID DERIVATIVES;315
13.5;5.5 a-HALOGENATION OF ACID DERIVATIVES;316
13.6;5.6 REACTION OF PHOSPHORIC ACID DERIVATIVES WITH ELECTROPHILES;319
13.7;5.7 a-ALKYLATION OF SULFONIC ACID DERIVATIVES;323
13.8;5.8 AROMATIC SUBSTITUTION;325
13.9;5.9 NUCLEOPHILIC ALLYLIC SUBSTITUTION;333
13.10;5.10 MISCELLANEOUS REACTIONS;336
13.11;REFERENCES;347
14;6.
ELECTROPHILIC RELATED ADDITION TO C=C;356
14.1;6.1 REDUCTION AND RELATED REACTIONS;357
14.2;6.2 ADDITION OF HALO-CONTAINING ADDENDS;371
14.3;6.3 BISAMINATION;375
14.4;6.4 ADDITION OF OXY-ADDENDS;375
14.5;6.5 CYCLOPROPANATION;384
14.6;6.6 CYCLOPROPENATION;400
14.7;6.7 AZIRIDINATION;400
14.8;6.8 ALKOXYSELENATION;402
14.9;6.9 RADICAL ADDITION;404
14.10;REFERENCES;417
15;7.
CONJUGATE ADDITION I;424
15.1;7.1 AUXILIARY ON DONOR NUCLEOPHILE – SIMPLE ADDITION;425
15.2;7.2 AUXILIARY ON DONOR NUCLEOPHILE – TANDEM ADDITION;473
15.3;REFERENCES;485
16;8.
CONJUGATE ADDITION II;490
16.1;8.1 AUXILIARY ON ACCEPTOR a,ß-UNSATURATED SYSTEM – SIMPLE ADDITION;491
16.2;REFERENCES;548
17;9.
CONJUGATE ADDITION III;552
17.1;9.1 a,ß-UNSATURATED ACYL DERIVATIVES – ADDITION OF HETERONUCLEOPHILES;553
17.2;9.2 OTHER ACTIVATED SYSTEMS;567
17.3;9.3 INTRAMOLECULAR REACTIONS;577
17.4;9.4 AUXILIARY ON a,ß-UNSATURATED SYSTEM – TANDEM ADDITION OFCARBON NUCLEOPHILES;579
17.5;9.5 AUXILIARY ON ACCEPTOR a,ß-UNSATURATED SYSTEM – TANDEM ADDITION OFHETERONUCLEOPHILES;590
17.6;9.6 AUXILIARY ON ACCEPTOR a,ß-UNSATURATED SYSTEM – RADICAL ADDITION;597
17.7;9.7 NUCLEOPHILIC ADDITION TO TRANSITION-METAL ALKENE/ARENE COMPLEXES;600
17.8;REFERENCES;604
18;10.
ADDITION TO C=N BONDS;608
18.1;10.1 REDUCTION OF IMINES, IMINIUM IONS, HYDRAZONES AND OXIMES;610
18.2;10.2 NUCLEOPHILIC ADDITION;612
18.3;10.3 RADICAL ADDITION;690
18.4;10.4 UGI COUPLING;693
18.5;REFERENCES;697
19;11.
ADDITION TO C=O BONDS I;702
19.1;11.1 REDUCTION;703
19.2;11.2 WITTIG & RELATED OLEFINATION;715
19.3;11.3 ADDITION OF ORGANOMETALLIC AND RELATED REAGENTS;720
19.4;REFERENCES;763
20;12. ADDITION TO C=O BONDS II;768
20.1;12.1 ADDITION OF ENOLATES (ALDOL AND RELATED REACTIONS);769
20.2;REFERENCES;848
21;13.
ADDITION TO C=O BONDS III;856
21.1;13.1 ADDITION OF ENOLATES (ALDOL AND RELATED REACTIONS);857
21.2;13.2 TANDEM REACTIONS;930
21.3;13.3 RADICAL REACTIONS;936
21.4;REFERENCES;942
22;14. CYCLOADDITIONS I;952
22.1;14.1 [2+2]-CYCLOADDITIONS;953
22.2;14.2 [3+2] CYCLOADDITIONS;970
22.3;REFERENCES;1014
23;15. CYCLOADDITIONS II;1018
23.1;15.1 [4+2]-INTERMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS) -AUXILIARY ON THE DIENOPHILE;1020
23.2;15.2 [4+2]-INTERMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS) -AUXILIARY ON THE DIENE;1067
23.3;15.3 [4+2]-INTRAMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS);1086
23.4;15.4 [4+2]-HETERO-CYCLOADDITIONS (HETERO-DIELS-ALDER REACTIONS);1090
23.5;15.5 [4+3] CYCLOADDITIONS;1115
23.6;15.6 [6+2] AND [6+4] CYCLOADDITIONS;1120
23.7;15.7 ELECTROCYCLIC REACTIONS;1120
23.8;REFERENCES;1124
24;16.
REARRANGEMENTS REACTIONS;1134
24.1;16.1 [2,3]-SIGMATROPIC VARIANTS;1135
24.2;16.2 [3,3]-SIGMATROPIC VARIANTS;1145
24.3;16.3 SUNDRY REARRANGEMENTS;1158
24.4;16.4 ENE REACTIONS;1166
24.5;REFERENCES;1174
25;17A. KINETIC RESOLUTION-RELATED PROCESSES;1180
25.1;17.1 SIMPLE KINETIC RESOLUTION;1181
25.2;17.2 CRYSTALLIZATION INDUCED DYNAMIC RESOLUTION;1182
25.3;17.3 DYNAMIC KINETIC RESOLUTION OF AUXILIARY-BEARING ELECTROPHILES;1183
25.4;17.4 DERACEMIZATION/DYNAMIC KINETIC RESOLUTION VIA ACYLATION-TYPEREACTIONS;1197
25.5;17.5 DESYMMETRIZATION OF MESO COMPOUNDS;1218
25.6;REFERENCES;1235
26;17B. MISCELLANEOUS REACTIONS;1238
26.1;17.6 TRANSITION-METAL CONTROLLED REACTIONS;1239
26.2;17.7 PHOTOCHEMICAL CYCLIZATIONS;1263
26.3;17.8 MISCELLANEOUS CYCLISATIONS;1265
26.4;17.9 SULFOXIDE PREPARATION FROM SULFIDES;1266
26.5;17.10 ELIMINATION REACTIONS;1267
26.6;17.11 BIO-TRANSFORMATIONS;1268
26.7;REFERENCES;1269

Leseproben

2 Alkylation and Related Reactions I
Abstract
This chapter deals initially with the alkylation and related reactions of carbanions based on allyl/benzyl systems, oxazolines, and formamidines. This is followed by simple and tandem reactions of carbanions from aldehydes and ketones via activated derivatives such as hydrazones, imines, and enamines. The foregoing processes introduce alkyl, amino, halogeno, hydroxyl, silyl, thio, phospinyl groups and lead to a wide array of optically pure products. Keywords
Nucleophilic substitutionaldehydeketoneoxazolineformamidinehydrazoneimineenaminealkylationaminationhalogenationhydroxylationsilylationphosphinylationthiolation 2.1 ALLYL AND BENZYL RELATED CARBANIONS 2.1.1 Isolated derivatives - Auxiliary on the nucleophile or electrophile 2.1.2 Nitrogen-containing derivatives 2.1.2.1 Aminooxazolines 2.1.2.2 Formamidines 2.1.2.3 Allyl systems 2.1.2.4 Benzyl systems 2.1.3 Oxygen derivatives - allyloxy and enol ether equivalents 2.1.4 Silicon-containing allyl and benzyl derivatives 2.2 ALLENIC ETHER TANDEM ACYLATION-CYCLIZATION 2.3 ALDEHYDE DERIVED NUCLEOPHILES 2.3.1 Simple aldehydes 2.3.1.1 a-Alkylation     2.3.1.1.1 Via hydrazone derivatives     2.3.1.1.2 Via imine and enamine derivatives 2.3.1.2 a-Hydroxylation and a-silylation     2.3.1.2.1 Sequential silylation + alkylation 2.3.1.4 a-Phosphinylation 2.3.2 a-Alkylation of a-heterosubstituted aldehydes 2.3.2.1 a-Amino derivatives 2.3.2.2 a-Oxy derivatives     2.3.2.2.1 Sequential alkylation + nucleophilic addition 2.3.2.3 a-Silyl derivatives – tandem alkylation + alkylation/acylation 2.3.2.4 a-Thio derivatives     2.3.2.4.1 Sequential alkylation + acylation 2.4 KETONE DERIVED NUCLEOPHILES 2.4.1 a-Alkylation 2.4.1.1 Acyclic systems with auxiliary on the ketone     2.4.1.1.1 Symmetrical derivatives     2.4.1.1.2 Unsymmetrical derivatives     2.4.1.1.3 ß-Dicarbonyl derivatives 2.4.1.2 Cyclic systems with auxiliary on the ketone     2.4.1.2.1 Cyclobutanone and cyclopentanone derivatives     2.4.1.2.2 Cyclohexanone derivatives     2.4.1.2.3 Higher order cyclic ketones     2.4.1.2.4 ß-Dicarbonyl derivatives 2.4.1.3 a-Heteroatom substituted ketones     2.4.1.3.1 a-Oxy substituted derivatives     2.4.1.3.2 a-Dicarbonyl and related derivatives     2.4.1.3.3 a-Nitronate substituted derivatives     2.4.1.3.4 a-Silyl substituted derivatives     2.4.1.3.5 a-Thio substituted derivatives     2.4.1.3.6 a,a'-Diamino substituted derivatives     2.4.1.3.7 a,a'-Dioxy substituted derivatives 2.4.2 Reaction with other electrophiles 2.4.2.1 a-Acylation, a-Amination, and a-Hydroxylation 2.4.2.2 a-Silylation     2.4.2.2.1 Sequential silylation + alkylation 2.4.2.3 a-Phosphinylation, a-Thiolation, and a-Halogenation 2.5 ALDEHYDE AND KETONE ENOLATES WITH AUXILIARY-CONTAINING ELECTROPHILES 2.5.1 Alkylation, acylation, and amination REFERENCES References
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