Key Chiral Auxiliary Applications -  Gregory Roos

Key Chiral Auxiliary Applications (eBook)

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2014 | 2. Auflage
1270 Seiten
Elsevier Science (Verlag)
978-0-12-417115-2 (ISBN)
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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.
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

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

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 α-Alkylation

    2.3.1.1.1 Via hydrazone derivatives

    2.3.1.1.2 Via imine and enamine derivatives

2.3.1.2 α-Hydroxylation and α-silylation

    2.3.1.2.1 Sequential silylation + alkylation

2.3.1.4 α-Phosphinylation

2.3.2 α-Alkylation of α-heterosubstituted aldehydes

2.3.2.1 α-Amino derivatives

2.3.2.2 α-Oxy derivatives

    2.3.2.2.1 Sequential alkylation + nucleophilic addition

2.3.2.3 α-Silyl derivatives – tandem alkylation + alkylation/acylation

2.3.2.4 α-Thio derivatives

    2.3.2.4.1 Sequential alkylation + acylation

2.4 KETONE DERIVED NUCLEOPHILES

2.4.1 α-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 β-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 β-Dicarbonyl derivatives

2.4.1.3 α-Heteroatom substituted ketones

    2.4.1.3.1 α-Oxy substituted derivatives

    2.4.1.3.2 α-Dicarbonyl and related derivatives

    2.4.1.3.3 α-Nitronate substituted derivatives

    2.4.1.3.4 α-Silyl substituted derivatives

    2.4.1.3.5 α-Thio substituted derivatives

    2.4.1.3.6 α,α′-Diamino substituted derivatives

    2.4.1.3.7 α,α′-Dioxy substituted derivatives

2.4.2 Reaction with other electrophiles

2.4.2.1 α-Acylation, α-Amination, and α-Hydroxylation

2.4.2.2 α-Silylation

    2.4.2.2.1 Sequential silylation + alkylation

2.4.2.3 α-Phosphinylation, α-Thiolation, and α-Halogenation

2.5 ALDEHYDE AND KETONE ENOLATES WITH AUXILIARY-CONTAINING ELECTROPHILES

2.5.1 Alkylation, acylation, and amination

REFERENCES

References


1.PippelD.J.CurtisM.D.DuH.BeakP.J Org Chem1998632

2.GiardináA.MecozziT.PetriniM.J Org Chem2000658277

3.KardassisG.BrungsP.NothhelferC.SteckhanE.Tetrahedron1998543479

4.PasquarelloA.PoliG.PotenzaD.ScolasticoC.Tetrahedron:...

Erscheint lt. Verlag 20.1.2014
Sprache englisch
Themenwelt Naturwissenschaften Chemie Organische Chemie
Naturwissenschaften Chemie Technische Chemie
Technik
ISBN-10 0-12-417115-X / 012417115X
ISBN-13 978-0-12-417115-2 / 9780124171152
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