A Modular Dual‐Catalytic Aryl‐Chlorination of Alkenes

Abstract

Alkyl chlorides are a class of versatile building blocks widely used to generate C(sp3)‐rich scaffolds through transformation such as nucleophilic substitution, radical addition reactions and metal‐catalyzed cross‐coupling processes. Despite their utility in the synthesis of high‐value functional molecules, distinct methods for the preparation of alkyl chlorides are underrepresented. Here, we report a visible‐light‐mediated dual catalysis strategy for the modular synthesis of highly functionalized and structurally diverse arylated chloroalkanes via the coupling of diaryliodonium salts, alkenes and potassium chloride. A distinctive aspect of this transformation is a ligand‐design‐driven approach for the development of a copper(II)‐based atom‐transfer catalyst that enables the aryl‐chlorination of electron‐poor alkenes, complementing its iron(III)‐based counterpart that accommodates non‐activated aliphatic alkenes and styrene derivatives. The complementarity of the two dual catalytic systems allows the efficient aryl‐chlorination of alkenes bearing different stereo‐electronic properties and a broad range of functional groups, maximizing the structural diversity of the 1‐aryl, 2‐chloroalkane products.