Colvin / Perlmutter / Buckommgham Silicon in Organic Synthesis

Butterworths Monographs in Chemistry and Chemical Engineering
1. Auflage 2013
ISBN: 978-1-4831-4223-4
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 360 Seiten, Web PDF

Silicon in Organic Synthesis provides an introduction to the organic chemistry of silicon. This book places particular emphasis on the concept of silicon as a 'ferryman, mediating the transformation of one wholly organic molecule into another. The book begins by reviewing the discovery and development of organosilicon compounds. This is followed by separate chapters on the physical properties of organosilicon compounds; the preparation of a-metallated organosilanes, which play a key role in preparative organosilicon chemistry; migration/rearrangement reactions of silicon; the preparation and chemistry of vinylsilanes, allylsilanes, arylsilanes, and organosilyl metallic compounds. Subsequent chapters cover the synthesis of compounds such as alkene, alkynylsilanes, allenylsilanes, silylketenes, alkyl silyl ethers, acyloxysilanes, and silyl enol ethers. This book aims to serve as a timely introduction to organic chemistry for students and practitioners of synthetic organic chemistry, as well as provide a source of useful information and possibly of new ideas to those already experienced in the area.

Autoren/Hrsg.

Colvin, Ernest W.

Perlmutter, Patrick

Buckommgham, A D

Danishefsky, S.

Inhaltsverzeichnis

1;Front Cover;1
2;Silicon in Organic Synthesis;4
3;Copyright Page;5
4;Table of Contents;10
5;Preface;6
6;Dedication;7
7;Abbreviations;8
8;Chapter 1. Introduction;14
8.1;References;15
9;Chapter 2. Physical properties of organosilicon compounds;17
9.1;2.1 Relative bond strengths;17
9.2;2.2 Electronegativity;18
9.3;2.3 p-Orbitals;20
9.4;2.4 d-Orbitals;23
9.5;References;26
10;Chapter 3. The ß-effect;28
10.1;References;32
11;Chapter 4. a-Metallated organosilanes;34
11.1;4.1 Organometallic addition to vinylsilanes;34
11.2;4.2 Proton abstraction;35
11.3;4.3 Metal–halogen exchange;38
11.4;4.4 Transmetallation;38
11.5;References;41
12;Chapter 5. Rearrangement reactions with migration of silicon;43
12.1;5.1 1,2- Rearrangements;43
12.2;5.2 1,3-Rearrangements;46
12.3;5.3 1,4-Rearrangements;50
12.4;5.4 1,5-Rearrangements;50
12.5;References;51
13;Chapter 6. Organohalogenosilanes and substitution at silicon;53
13.1;References;56
14;Chapter 7. Vinylsilanes;57
14.1;7.1 Preparation;58
14.2;7.2 Geometric differentiation;73
14.3;7.3 Reactivity;75
14.4;7.4 Some other reactions of vinylsilanes;89
14.5;7.5 Addendum;92
14.6;References;93
15;Chapter 8. aß-Epoxysilanes as precursors of carbonyl compounds and heteroatom-substituted alkenes;96
15.1;8.1 Preparation;96
15.2;8.2 Isomerization;97
15.3;References;108
16;Chapter 9. Allylsilanes;110
16.1;9.1 Preparation;111
16.2;9.2 Electrophilic substitution;117
16.3;9.3 Other selected examples of silyl control of carbonium ion formation and collapse;130
16.4;9.4 Some reactions not involving carbonium ions;131
16.5;9.5 Addendum;133
16.6;References;135
17;Chapter 10. Arylsilanes;138
17.1;10.1 Preparation;138
17.2;10.2 Electrophile-induced desilylation;139
17.3;References;145
18;Chapter 11. Organosilyl anions;147
18.1;11.1 Preparation;147
18.2;11.2 Reactions;149
18.3;References;152
19;Chapter 12. Alkene synthesis by 1,2-elimination reactions of ß-functional organosilanes;154
19.1;12.1 ß-Hydroxyalkylsilanes;155
19.2;12.2 ß-HalogenoalkylsiIanes and related species;165
19.3;12.3 Addendum;173
19.4;References;175
20;Chapter 13. Alkynyl- and allenyl-silanes;178
20.1;13.1 Alkynylsilanes;178
20.2;13.2 Allenylsilanes;183
20.3;References;185
21;Chapter 14. Silylketenes;187
21.1;References;190
22;Chapter 15. Alkyl silyl ethers;191
22.1;15.1 Solvolysis;191
22.2;15.2 Trimethylsilyl ethers, ROSiMe3;192
22.3;15.3 t-Butyldimethylsilyl ethers, ROSiMe2But, and related species;197
22.4;15.4 Addendum;202
22.5;References;203
23;Chapter 16. Acyloxysilanes (silyl carboxylates);206
23.1;References;209
24;Chapter 17. Silyl enol ethers and silyl ketene acetals;211
24.1;17.1 Preparation of silyl enol ethers;211
24.2;17.2 Preparation of silyl ketene acetals;226
24.3;17.3 Reactions;228
24.4;17.4 Addendum;289
24.5;References;293
25;Chapter 18. Trimethylsilyl-based reagents;301
25.1;18.1 Reagent preparation;302
25.2;18.2 Ester and ether cleavage;304
25.3;18.3 Carbonyl addition processes;308
25.4;18.4 Some other addition processes;317
25.5;18.5 Some other functionalized silane reagents;317
25.6;18.6 Addendum;320
25.7;References;323
26;Chapter 19. Nitrogen-substituted silanes;327
26.1;19.1 Amino-silanes;327
26.2;19.2 Oxidative decyanation;329
26.3;19.3 Amides and amide bond formation;329
26.4;References;332
27;Chapter 20. Silicon-substituted bases and ligands;334
27.1;References;337
28;Chapter 21. Silanes as reducing agents;338
28.1;21.1 Hydrosilylation;338
28.2;21.2 Ionic hydrogenation;342
28.3;21.3 Reductive silylation;344
28.4;21.4 Deoxygenation processes;346
28.5;References;347
29;Index;350