Recent Developments in Organic Synthesis with 1-Haloalkyl Aryl Sulfoxides

Abstract

This account deals with recent developments in organic synthesis with 1-haloalkyl aryl sulfoxides, especially with 1-chloroalkyl aryl sulfoxides. 1-Chloroalkyl aryl sulfoxides are quite easily prepared from alkyl aryl sulfides. Sulfinyl carbanions and sulfinylated carbon radicals can easily be generated from 1-chloroalkyl aryl sulfoxides. The sulfinyl carbanions were added to carbonyl compounds to give the adducts, from which various kinds of new carbonyl compounds with carbon homologation were synthesized. Optically active 1-chloroalkyl p-tolyl sulfoxides were obtained from optically active (-)-chloromethyl p-tolyl sulfoxide. Asymmetric syntheses of epoxides, α-amino aldehydes, aziridines, α-hydroxy acids and their derivatives, and propargylic alcohols were realized starting from the optically active (-)-1-chloroalkyl p-tolyl sulfoxides. 1.Introduction 2.Synthesis of 1-Haloalkyl Aryl Sulfoxides 3.Organic Synthesis with 1-Haloalkyl Aryl Sulfoxides 4.Organic Synthesis with Sulfinyloxiranes 4.1.Reaction of Sulfinyloxiranes under Heating or with Lewis Acids 4.2.Reaction of Sulfinyloxiranes with Benzeneselenolate and Thiolates 4.3. Reaction of Sulfinyloxiranes with Amines, Cesium Acetate, and Metal Halides 4.4. Reaction of Sulfinyloxiranes with Alkylmetals 5.Asymmetric Synthesis with Optically Active (-)-1-Chloroalkyl p-Tolyl Sulfoxides 5.1. Preparation of Optically Active Sulfinyloxiranes and a Synthesis of Optically Active Epoxides, α-Amino Aldehydes, and Aziridines 5.2. Asymmetric Synthesis of Both Enantiomers of α-Hydroxy Acids, Esters, Amides, and Propargylic Alcohols 6. Conclusion