Reactions of 2-(α-Haloalkyl)thiiranes with nucleophilic reagents: V. Reactions of 2-(α-Chloroalkyl)thiiranes with organolithium compounds

2-(α-Haloalkyl)thiiranes reacted with methyl-, butyl-, and phenyllithium to give the corresponding allyl sulfides. The reactions of diastereoisomeric erythro- and threo-2-(1-chloroethyl)thiiranes with phenyllithium were stereospecific, and they afforded (E)- and (Z)-1-phenylsulfanylbut-2-enes, respectively. 3-Chloromethyl-2,2-dimethylthiirane and phenyllithium gave rise to a mixture of 3-methyl-3-phenylsulfanylbut-1-ene and 3-methyl-1-phenylsulfanylbut-2-ene. The reactions of 2-chloromethylthiiranes with phenyllithium and methyllithium in the presence of a catalytic amount of copper(I) iodide (10 mol %) led to the formation of substituted thiiranes as the major products. Mechanisms of the observed transformations are discussed.