Allyl sulphoxides chiral

A detailed study of the mechanism of the allyl sulphoxide-sulphenate rearrangement and its uses in synthesis has been reported. Rates of steroidal allyl sulphoxide rearrangements are influenced by chirality at sulphur, and configurational aspects established for compounds of this... 

The formation of a- and 9-allylated sulphides by the Pummerer-type reaction of vinylic sulphoxides with allylmagnesium bromide has been reported by Iwata et al. Monoallylation and diallylation can take place, depending on the bulkiness of the yS-substituent, and both acyclic and cyclic vinyl sulphoxides undergo the reaction. This method offers applicability to asymmetric synthesis using sulfinyl chirality. 

A full paper on the asymmetric synthesis of polyols using chiral allylic -hydroxy sulphoxides has been published (see Vol.21, p. 172). 

Acyclic Alditols.- A new approach to the synthesis of optically pure polyhydroxylated compounds by i) the stereospecific reduction of chiral -ketosulphoxides and ii) the stereospecific liydroxylation of chiral allylic /9-hydroxysulphoxides has been described. Thus the unsaturated ester (1) gave the chiral sulphoxide (2), which was sequentially reduced, hydtoxylated, and further reduced as outlined in Scheme 1 to give the L-arabinitol derivative (3) and hence penta-0-acetyl-L-arabinitol in high yield enantiomers are available by appropriate choice of the sulphoxide reagent. ... 

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