Ligand‐Controlled Regiodivergent and Enantioselective Copper‐Catalyzed Hydroallylation of Alkynes

A ligand‐controlled regiodivergent and enantioselective copper‐catalyzed intermolecular hydroallylation of alkynes with allylic phosphates and hydrosilanes has been achieved for the first time. The chiral bidentate sulfonate‐containing N‐heterocyclic carbene ligated CuCl complex leads to enantioenriched S N 2′‐type products, whereas the use of the IMesCuCl catalyst affords S N 2‐type products. Thus a range of chiral branched and achiral linear 1,4‐dienes could be facilely synthesized from readily available alkynes in a regiodivergent manner.