Mechanism and Scope of the Base-Induced Dehalogenation of (E)-Diiodoalkenes

Abstract

A wide range of nucleophiles have induced the elimination of iodine from (E)-diiodoalkenes to form alkynes under surprisingly mild conditions. The iodide anion is particularly efficient, and can drive the reaction to completion in less than 1 hour at room temperature in a polar aprotic solvent. Detailed investigations have suggested the reaction has a bimolecular polar mechanism. The deiodination reaction can be driven to completion with 1 equiv. of nucleophile and is partially catalytic with substoichiometric amounts of deiodinating reagent. Kinetic analysis of the stoichiometric iodide-induced reaction indicated an overall pseudo-first-order behavior. The reaction exhibited strong solvent effects, with much slower reactions observed in protic solvents than in polar aprotic solvents. The substrate dimethyl (2E)-2,3-diiodobutene-2-dioate demonstrated orthogonal reactivity for either elimination or hydrolysis, depending on the solvent and nucleophile used. This reaction is a major pathway for all the diiodoalkenes examined, and represents a challenge and an opportunity for using these substrates in organic synthesis.