Next‐Generation D 2 ‐Symmetric Chiral Porphyrins for Cobalt(II)‐Based Metalloradical Catalysis: Catalyst Engineering by Distal Bridging

Novel D 2 ‐symmetric chiral amidoporphyrins with alkyl bridges across two chiral amide units on both sides of the porphyrin plane (designated “HuPhyrin”) have been effectively constructed in a modular fashion to permit variation of the bridge length. The Co II complexes of HuPhyrin, [Co(HuPhyrin)], represent new‐generation metalloradical catalysts where the metal‐centered d‐radical is situated inside a cavity‐like ligand with a more rigid chiral environment and enhanced hydrogen‐bonding capability. As demonstrated with cyclopropanation and aziridination as model reactions, the bridged [Co(HuPhyrin)] functions notably different from the open catalysts, exhibiting significant enhancement in both reactivity and stereoselectivity. Furthermore, the length of the distal alkyl bridge can have a remarkable influence on the catalytic properties.