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8450642 
Journal Article 
Cyclization of γδ-unsaturated sulphenic acids to give thietan 1-oxide derivatives. Crystal structure of rel-(1R,2S,3R,4R)-3-hexyl-2- hydroxymethyl-4-methylthietan 1-oxide 
Neville Jones, D; Kogan, TP; Murray-Rust, P; Murray-Rust, J; Newton, RF 
1982 
Journal of the Chemical Society, Perkin Transactions 1
ISSN: 1472-7781
EISSN: 1364-5463 
1325-1332 
English 
erythro- and threo-2-t-Butylthio-3-vinylnonan-1-ol have been prepared by Claisen rearrangement of the silylketen acetals derived from (E)-non-2-enyl t-butylthioacetate followed by reduction with lithium aluminium hydride. The sulphur function influenced the stereoselectivity of formation of the silylketen acetals which, in turn, determined the ratio of diastereoisomeric products obtained in the rearrangement. Thermolysis of erythro-2-t-butylsulphinyl-3- vinylnonan-1-ol at 140 °C for 5 min gave erythro-1-(hydroxymethyl)-2- vinyloctanesulphenic acid which cyclized spontaneously to a mixture of rel-(1R,2R,3S,4R)- and rel-(1R,2S,3R,4R)-3-hexyl-2-(hydroxymethyl)-4- methylthietan 1-oxide. threo-2-Butylsulphinyl-3-vinylnonan-1-ol under the same conditions gave a mixture of rel-(1R,2R,3R,4R)- and rel-(1R,2S,3S,4R)-3-hexyl-2- (hydroxymethyl)-4-methylthietan 1-oxide. Allocations of configuration to these thietan 1-oxide derivatives based on transition-state considerations have been substantiated by a determination of the crystal structure of the rel-(1R,2S,3R,4R)-isomer and by n.m.r. spectroscopy, which also led to tentative assignments of conformation.