环丙烷化
卟啉
钴
催化作用
立体选择性
酰胺
化学
烷基
配体(生物化学)
桥联配体
金属
立体化学
材料科学
高分子化学
有机化学
光化学
受体
生物化学
作者
Yang Hu,Kai Lang,Jingran Tao,McKenzie K. Marshall,Qigan Cheng,Xin Cui,Łukasz Wojtas,X. Peter Zhang
标识
DOI:10.1002/anie.201812379
摘要
Novel D2 -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 CoII 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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