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 SN 2'-type products, whereas the use of the IMesCuCl catalyst affords SN 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.