
Silicon in Organic Synthesis
Butterworths Monographs in Chemistry and Chemical Engineering
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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 α-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.
Table of Contents
1 Introduction
2 Physical Properties of Organosilicon Compounds
2.1 Relative Bond Strengths
2.2 Electronegativity
2.3 p-Orbitals
2.4 P-Orbitals
3 The β-Effect
4 α-Metallated Organosilanes
4.1 Organometallic Addition to Vinylsilanes
4.2 Proton Abstraction
4.3 Metal-Halogen Exchange
4.4 Transmetallation
5 Rearrangement Reactions with Migration of Silicon
5.1 1,2-Rearrangements
5.2 1,3-Rearrangements
5.3 1,4-Rearrangements
5.4 1,5-Rearrangements
6 Organohalogenosilanes and Substitution at Silicon
7 Vinylsilanes
7.1 Preparation
7.2 Geometric Differentiation
7.3 Reactivity
7.4 Some other Reactions of Vinylsilanes
7.5 Addendum
8 αβ-Epoxysilanes as Precursors of Carbonyl Compounds and Heteroatom-Substituted Alkenes
8.1 Preparation
8.2 Isomerization
9 Allylsilanes
9.1 Preparation
9.2 Electrophilic Substitution
9.3 Other Selected Examples of Silyl Control of Carbonium Ion Formation and Collapse
9.4 Some Reactions not Involving Carbonium Ions
9.5 Addendum
10 Arylsilanes
10.1 Preparation
10.2 Electrophile-Induced Desilylation
11 Organosilyl Anions
11.1 Preparation
11.2 Reactions
12 Alkene Synthesis by 1,2-Elimination Reactions of β-Functional Organosilanes
12.1 β-Hydroxyalkylsilanes
12.2 β-Halogenoalkylsilanes and Related Species
12.3 Addendum
13 Alkynylsilanes and Allenylsilanes
13.1 Alkynylsilanes
13.2 Allenylsilanes
14 Silylketenes
15 Alkyl Silyl Ethers
15.1 Solvolysis
15.2 Trimethylsilyl Ethers
15.3 t-Butyldimethylsilyl Ethers
15.4 Addendum
16 Acyloxysilanes (Silyl Carboxylates)
17 Silyl Enol Ethers and Silyl Ketene Acetals
17.1 Preparation of Silyl enol Ethers
17.2 Preparation of Silyl Ketene Acetals
17.3 Reactions
17.3.1 Generation of Specific Enolate Anions
17.3.2 Lewis Acid-Catalysed Alkylation
17.3.3 Alkylation and α-Methylenation
17.3.4 Hydroxyalkylation and Related Reactions
17.3.5 Silyl Dienol Ethers and Bis(Silylenol) Ethers
17.3.6 Acylation
17.3.7 Hydroboration-Oxidation
17.3.8 Oxidation
17.3.9 Cycloaddition
17.3.10 Sigmatropic Rearrangements and Related Processes
17.3.11 Modified Acyloin Condensations and Related Reactions
17.3.12 1-Trimethylsilyl Trimethylsilyl Enol Ethers
17.3.13 Silyl Nitronates
17.4 Addendum
18 Trimethylsilyl-Based Reagents
18.1 Reagent Preparation
18.2 Ester and Ether Cleavage
18.3 Carbonyl Addition Processes
18.4 Other Addition Processes
18.5 Other Functionalized Silane Reagents
18.6 Addendum
19 Nitrogen-Substituted Silanes
19.1 Amino-Silanes
19.2 Oxidative Decyanation
19.3 Amides and Amide Bond Formation
20 Silicon-Substituted Bases and Ligands
21 Silanes as Reducing Agents
21.1 Hydrosilylation
21.2 Ionic Hydrogenation
21.3 Reductive Silylation
21.4 Deoxygenation Processes
Index
Product details
- No. of pages: 360
- Language: English
- Copyright: © Butterworth-Heinemann 1981
- Published: January 1, 1981
- Imprint: Butterworth-Heinemann
- eBook ISBN: 9781483142234
About the Author
Ernest W. Colvin
About the Editors
J E Baldwin
Patrick Perlmutter is Adjunct Professor of Chemistry at La Trobe University in Australia. He has been a university academic for 35 years with a highly active research group specialising in synthesis and new synthetic methods including conjugate additions, catalysis, total synthesis, medicinal chemistry and chemical biology. His research group has generated approximately 200 peer-reviewed publications in that time.
Affiliations and Expertise
Adjunct Professor of Chemistry
La Trobe University, Australia