Cobalt‐Catalyzed Diastereo‐ and Enantioselective Hydroalkylation of Cyclopropenes with Cobalt Homoenolates

Abstract Catalylic diastereo‐ and enantioselective hydroalkylation of 3,3‐disubstituted cyclopropenes with Co‐homoenolate generated in situ from ring‐opening of easily accessible cyclopropanols promoted by a chiral phosphine–cobalt complex is presented. Such a process represents the unprecedented and direct introduction of a wide range of functionalized alkyl groups without the need of pre‐formation of stoichiometric amounts of organometallic reagents onto the cyclopropane motif, affording multi‐substituted cyclopropanes in up to 99 % yield with >95:5 dr and 98:2 er. Functionalization of the products delivered enantioenriched cyclopropanes that are otherwise difficult to access.