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 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
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- © Butterworth-Heinemann 1981
- 1st January 1981
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