A general and efficient cobalt(II)-based catalytic system for highly stereoselective cyclopropanation of alkenes with α-cyanodiazoacetates.

[Co(P1)], the cobalt(II) complex of the D(2)-symmetric chiral porphyrin 3,5-Di(t)Bu-ChenPhyrin, is an effective catalyst for catalyzing asymmetric olefin cyclopropanation with the acceptor/acceptor-type diazo reagent α-cyanodiazoacetates. The [Co(P1)]-catalyzed reaction is versatile and suitable for both aromatic and aliphatic olefins with varied electronic properties, including electron-rich and -poor olefins. The Co(II)-based catalytic system can be operated in a one-time protocol under mild conditions, affording the desired cyclopropane products in high yields with both high diastereo- and enantioselectivity. The resulting enantiomerically enriched 1,1-cyclopropanenitrile esters provide convenient access to a number of densely functionalized chiral cyclopropane derivatives, including α-cyclopropyl-β-amino acids.