Bifunctional iron-mediated multicomponent Markovnikov-selective radical hydrothiolation of alkenes

Abstract

Direct (utilizing easily available and abundant raw materials) and selective hydrofunctionalization of alkenes is an appealing method for simplifying chemical synthesis. Dithiocarbamates have gained increasing prominence in medicine and agrochemistry. Herein, we report an iron-mediated multicomponent Markovnikov hydrothiolation of alkenes to afford dithiocarbamates with good yields. This mild strategy avoids the preparation of thiolation reagents and shows excellent functional group tolerance. The synthetic utility of this transformation was demonstrated by gram-scale synthesis and late-stage modification of various drug and bioactive molecules. Mechanistic studies show that the reaction involves an iron catalyzed hydrogen atom transfer and a single electron transfer process. Iron salts play a dual role, hitting two birds with one stone.