Nickel‐Catalyzed Asymmetric Hydroaryloxy‐ and Hydroalkoxycarbonylation of Cyclopropenes

The asymmetric Reppe carbonylation reactions provide a straightforward access to α‐chiral carbonyl compounds. The reported paradigms predominantly adopted precious palladium as the catalyst. Here we report a nickel‐catalyzed asymmetric carbonylation of cyclopropenes with phenyl formate and CO/ROH, respectively. This asymmetrical synthetic protocol features high atom economy, good functional group tolerance, which rapidly constructs polysubstituted cyclopropanecarboxylic derivatives with excellent diastereo‐ and enantioselectivity. The synthetic utility is demonstrated by facile conversion of the chiral products into bioactive molecules such as (−)‐Tranylcypromine and (−)‐Lemborexant. Highly enantioselective inter‐ and intramolecular Ni‐catalyzed hydroalkoxycarbonylation yields various enantioenriched polysubstituted cyclopropanecarboxylic derivatives with quaternary carbon stereocenters.