Reactions potentially related to coenzyme B12 dependent rearrangements: observations on the radical [1,2]-acyl and -thiol ester migrations

Abstract

Reaction of 2-iodomethyl-2-methyl-3-oxo estars with tributyltin radicals, generated, photochemically, from hexabutylditin or tributyltin hydride in cyclohexane, or benzene–acetonitrile, resulted in a [1,2]-acyl migration in 10–63% yields dependent on the source of tin radical and substrate used. Radical migration was confirmed by the use of tributyltin deuteride. Thiol ester group migration was not observed. A new, highly efficient method for thiol ester synthesis is described.