Formation and X-ray structural study of enantiopure fused 1,5-oxathiocane derivatives

Abstract

The reaction of (E,R_S)-3-[(1S)-isoborneol-10-sulf inyl]-1-methoxybuta-1,3-diene 1 with benzaldehyde or p-nitrobenzaldehyde, when carried out in dichloromethane in the presence of trimethylsilyl trifluoromethanesulfonate, leads mainly to enantiopure condensed 2-aryl-4-ethylidene-1,5-oxathiocane S-oxides. The reaction path begins with the ionic addition of the enantiopure diene 1 onto the C=O group activated by trimethylsilyl cation attack on the carbonyl oxygen. The almost complete diastereoselection observed in the following closure of the eight-membered ring is interpreted as being a consequence of the conformational control on cyclization which leads to the thermodynamically favoured isomer. The crystal structure of the 2,4-dinitrophenylhydrazone of the α,β-unsaturated aldehyde 5, obtained by reacting diene 1 with p-nitrobenzaldeyde, supports the stereochemical results.

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