Reductive Alkylation of Enamines with Chloromethyl p‐Tolyl Sulfone via a Radical Chain Process

Cyclic cnamines can be alkylatcd diastereoselectively with chloromethyl p-tolylsulfone. The cis-selectivity of this radical reaction is especially striking in the formation of cyclohexane derivatives such as 1 (>95%). The rate at which p-tolylsulfonylmethyl radical adds to the enamine is a function both of its donor characteristics and of steric factors.