Silicon in Organic Synthesis

Butterworths Monographs in Chemistry and Chemical Engineering

1st Edition - January 1, 1981

Author: Ernest W. Colvin

Editors: Patrick Perlmutter, A D Buckommgham, S Danishefsky

eBook ISBN:

9 7 8 - 1 - 4 8 3 1 - 4 2 2 3 - 4

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,”… Read more

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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.

1 Introduction2 Physical Properties of Organosilicon Compounds 2.1 Relative Bond Strengths 2.2 Electronegativity 2.3 p-Orbitals 2.4 P-Orbitals3 The β-Effect4 α-Metallated Organosilanes 4.1 Organometallic Addition to Vinylsilanes 4.2 Proton Abstraction 4.3 Metal-Halogen Exchange 4.4 Transmetallation5 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-Rearrangements6 Organohalogenosilanes and Substitution at Silicon7 Vinylsilanes 7.1 Preparation 7.2 Geometric Differentiation 7.3 Reactivity 7.4 Some other Reactions of Vinylsilanes 7.5 Addendum8 αβ-Epoxysilanes as Precursors of Carbonyl Compounds and Heteroatom-Substituted Alkenes 8.1 Preparation 8.2 Isomerization9 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 Addendum10 Arylsilanes 10.1 Preparation 10.2 Electrophile-Induced Desilylation11 Organosilyl Anions 11.1 Preparation 11.2 Reactions12 Alkene Synthesis by 1,2-Elimination Reactions of β-Functional Organosilanes 12.1 β-Hydroxyalkylsilanes 12.2 β-Halogenoalkylsilanes and Related Species 12.3 Addendum13 Alkynylsilanes and Allenylsilanes 13.1 Alkynylsilanes 13.2 Allenylsilanes14 Silylketenes15 Alkyl Silyl Ethers 15.1 Solvolysis 15.2 Trimethylsilyl Ethers 15.3 t-Butyldimethylsilyl Ethers 15.4 Addendum16 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 Addendum18 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 Addendum19 Nitrogen-Substituted Silanes 19.1 Amino-Silanes 19.2 Oxidative Decyanation 19.3 Amides and Amide Bond Formation20 Silicon-Substituted Bases and Ligands21 Silanes as Reducing Agents 21.1 Hydrosilylation 21.2 Ionic Hydrogenation 21.3 Reductive Silylation 21.4 Deoxygenation ProcessesIndex