Copper‐Catalyzed Chemo‐ and Enantioselective Radical 1,2‐Carbophosphonylation of Styrenes

Abstract

AbstractThe copper‐catalyzed enantioselective radical difunctionalization of alkenes from readily available alkyl halides and organophosphorus reagents possessing a P−H bond provides an appealing approach for the synthesis of α‐chiral alkyl phosphorus compounds. The major challenge arises from the easy generation of a P‐centered radical from the P−H‐type reagent and its facile addition to the terminal side of alkenes, leading to reverse chemoselectivity. We herein disclose a radical 1,2‐carbophosphonylation of styrenes in a highly chemo‐ and enantioselective manner. The key to the success lies in not only the implementation of dialkyl phosphites with a strong bond dissociation energy to promote the desired chemoselectivity but also the utilization of an anionic chiral N,N,N‐ligand to forge the chiral C(sp3)−P bond. The developed Cu/N,N,N‐ligand catalyst has enriched our library of single‐electron transfer catalysts in the enantioselective radical transformations.