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

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2019 Jan 3

PMID 30601601

Citations 21

Authors

Yang Hu

Kai Lang

Jingran Tao

McKenzie K Marshall

Qigan Cheng

Xin Cui

Lukasz Wojtas

X Peter Zhang

Affiliations

Soon will be listed here.

Abstract

Novel D -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 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.

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