Mechanistic and stereochemical studies on Ferrier reaction by means of chirally deuterated glucose

Abstract

The mechanism of Ferrier reaction, cyclitol formation from 5-enopyranosides, was investigated by using (E)-selectively deuterated methyl [6-2H]-2,3,4-tri-O-benzyl-α-D-xylo-hex-5-enopyranoside. The overall reaction was non-stereoselective with respect to the C-6 position of the substrate. Crucial organomercurial intermediates were isolated and characterized. The loss of stereochemical integrity was attributed mainly to the formation of an open-chain organomercurial and its rapid equilibrium. A mechanism involving radical intermediate is suggested. © 1994.