Iodide reagent controlled reaction pathway of iodoperoxidation of alkenes: a high regioselectivity synthesis of α- and β-iodoperoxidates under solvent-free conditions

Abstract

A highly atom economical, efficient and environmentally friendly iodoperoxidation of alkenes with tert-butyl hydroperoxide (TBHP) and iodide/iodine is reported in this paper. This method afforded a convenient path to obtain two different configurations of iodoperoxidates from the same starting materials. Notably, the regiodivergent iodoperoxidation reaction was achieved by using different iodide reagents. A series of control experiments were performed, which suggested the involvement of a radical pathway for the anti-Markovnikov type iodoperoxidates (α) in the combination of ammonium iodide (NH₄I)/TBHP, and an active cationic iodine pathway for the Markovnikov type adduct (β) with iodine (I₂) and TBHP.