Trans-Diastereoselective Syntheses of γ-Lactones by Visible Light-Iodine-Mediated Carboesterification of Alkenes.

Abstract

This study aims to develop an intermolecular lactonization reaction of alkenes with carbonyls mediated by visible light and molecular iodine. The one-step reaction involved the carboesterification of alkenes to produce the corresponding lactones in moderate to good yield. It was also revealed that it is possible to control the diastereoselectivity of the reaction by altering the base used and the reaction conditions. When water was added as a solvent, the reaction resulted in the formation of lactones with trans-selectivity. A mechanistic investigation was undertaken and it was found that the reaction requires the generation of an iodine radical from molecular iodine, driven by visible light irradiation, and proceeds via the formation of an iodine radical alkene adduct. The proposed reaction is an example of a rare-metal free intermolecular addition cyclization reaction, which is an environment-friendly chemical process that only uses molecular iodine. In addition, since diastereoselectivity was observed without the use of any specific reagents, the developed methodology is an example of a novel stereoselective transformation using only cost-effective reagents.