Silicon in Organic Synthesis

Silicon in Organic Synthesis

Butterworths Monographs in Chemistry and Chemical Engineering

1st Edition - January 1, 1981

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  • Author: Ernest W. Colvin
  • eBook ISBN: 9781483142234

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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


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

A D Buckommgham

S Danishefsky

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