Nitrile Synthesis. The Use of Corey-Kim System as Dehydrant of Aldoximes

Abstract

In 1972 Corey and Kim^2,3 described a method for selective oxidation of alcohols by chlorosulfonium salts. Exceptions are allylic and benzylic alcohols which yield the corresponding halides.⁴ Very recently, reagents derived from an insoluble polymer support⁵ have been developed. With the latter, selective monooxidation of α, ω-diols becomes feasible. We were interested in the reaction of aldoximes with dimethylchlorosulfonium salts on the premise that one or two synthetically useful processes could evolve. The oximino sulfonium intermediate may be deprotonated

to give directly a nitrile and dimethyl sulfoxide; alternatively, it may lead ot an ylide wihich could undergo [3,2]- sigmatropic rearrangement ot afford the nitroso compiound and thence an α-methylthio oxime. The ylide could also act as the nitrile precursor.