One-Step Formation of Four Chemical Bonds toward Dithiophosphinates via Multicomponent Reaction

Abstract

A multicomponent reaction of diphenylphosphine, S₈, and alcohols has been developed for the efficient dehydrative synthesis of dithiophosphinates. This method enables the one-pot construction of four chemical bonds (S-C-P=S), delivering the target products with exclusive selectivity. It exhibits a broad substrate scope, accommodating a variety of allylic alcohols including challenging α-substituted branched allylic alcohols as well as linear primary and secondary ones, and can be readily extended to benzyl alcohols and even the less reactive aliphatic alcohols. Control experiments combined with Hammett plot analysis indicate that the high yields and excellent selectivity are governed by well-regulated generation of key intermediates such as phosphinodithioic acid, phosphine sulfide and carbocations and precise suppression of their potential side reactions.