Cobalt-catalysed enantioselective C(sp3)–C(sp3) coupling

Enantioselective C(sp3)–C(sp3) coupling substantially impacts organic synthesis but remains challenging. Cobalt has played an important role in the development of homogeneous organometallic catalysis, but there are few examples of its use in asymmetric cross-coupling. Here we report a cobalt-catalysed enantioselective C(sp3)–C(sp3) coupling reaction, namely, alkene hydroalkylation, to access chiral fluoroalkanes. This reaction represents a catalyst-controlled enantioselective coupling mode in which a tailor-made auxiliary is unnecessary; via this reaction, an aliphatic C–F stereogenic centre can be introduced at the desired position in an alkyl chain. Enantioselective C(sp3)–C(sp3) coupling plays an important role in organic synthesis, but limitations remain. Now, cobalt-catalysed enantioselective C(sp3)–C(sp3) coupling between achiral fluoroalkenes and alkyl halides enables the streamlined and auxiliary-free synthesis of chiral fluoroalkanes.