Organic Sulfur Mechanisms. 14. Kinetic Resolution in the Reaction of a Sulfene with an Amine

Abstract

The reaction of camphor-10-sulfonyl chloride (1) with menthylamine (2) is shown by deuterium exchange experiments to proceed principally via the sulfene and the kinetic resolution first observed by Read and Storey (1) demonstrated to arise in the sulfene trapping step. This work constitutes the first authenticated kinetic resolution by a sulfene and also provides new kinetic evidence complementary to earlier work for the existence of a sulfene in the reaction of an alkanesulfonyl chloride with an amine. Evidence is also presented that a small but clearly detectable amount of "unexchanged" product in the deuterium exchange reactions arises via a direct displacement of the amine on the sulfonyl chloride; no kinetic resolution in this latter process was detectable.