Enantioselective alkene hydroalkylation overcoming heteroatom constraints via cobalt catalysis

Alkene hydroalkylation enables efficient and selective formation of C(sp3)–C(sp3) bonds with unique advantages, such as exceptional chemoselectivity and remarkable tolerance of functional groups. However, eliminating the heteroatom-containing substrate-specific constraints in achieving precise enantioselectivity remains a challenge in alkene hydroalkylation reactions. Here we report the cobalt-hydride-catalysed enantioselective hydroalkylation of 1,1-disubstituted alkenes, enabling the efficient construction of chiral tertiary carbon centres at the benzyl position. The enantioselective control mode does not rely on Lewis basic or polar heteroatom functional groups; instead, an efficient stereochemical control environment is established between substrates and catalysts through weak C–H···π interactions in the alkene hydrometalation step. This work adds a differentiated case to the Giese-type addition reaction and metal-hydride-catalysed alkene hydroalkylation precedents towards breaking substrate-specific constraints in the enantioselective control mode. Eliminating the substrate-specific constraints in alkene hydroalkylation reactions, where heteroatom-containing substrates are often required to achieve enantioselectivity, remains a challenge. Now a cobalt-hydride catalyst is shown to overcome heteroatom constraints through C–H···π interactions between substrates and catalysts, enabling the efficient construction of chiral tertiary carbon centres at the benzyl position.