Some synthetic studies in organo-sulphur chemistry

Eldred, Colin David (1979) Some synthetic studies in organo-sulphur chemistry. University of Southampton, Doctoral Thesis.

Abstract

N-Sulphinylsulphonamides and sulphur diimides behave as enophiles inthe ene reactionl5, but little use has been made of this interesting property. Chapter One explores the synthetic potential of these 'imides of sulphur dioxide'. Ene adducts of several olefins with N,N'-bis (benzenesulphonyl) sulphur diimide and N-sulphinylbenzenesulphonamide were prepared, and alkylation of the ene adducts was attempted. The sulphur diimide ene adducts were transformed into allyl amines via [2,3]sigmatropic rearrangement, and the possibility of achieving a similar transformation of the N-sulphinylsulphonamide ene adducts to allyl alcohols was investigated. Farther applications of the N-sulphinylsulphonamide ene adducts were explored. Chapter Two describes a new approach to an x,p-unsaturated aryl anion or ff-acyl vinyl anion equivalent. Two general syntheses of 1-thiosubstituted 3-hydroxyprop-l-enes and some derived ethers were developed, and alkylation of the derived allyl or vinyl anions was studied. The at-lithiovinyl sulphide dianions derived from 3-hydroxy-l-phenylthioprop1-ene and 1 butylthio-3-hydroxyprop-l-ene provided a,)9 -unsaturated acyl anion equivalents. In Chapter Three, two new synthetic approaches to a spiro [4,5] decane ketone found in vetiver oil are described. The first of these involved a phenylthiovinyl cyclopropane to cyclopentene rearrangement as the spiro-cyclisation step; a synthesis of phenylthiovinyl cyclopropanes via alkylation of allyl sulphide anions was developed. The second approach proposed an intramolecular enolate alkylation as the spiro-cyclisation step, and utilised the chemistry of 1,3-dithianes to establish the requisite protected 1,4-dicarbonyl moeity.

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