在该文中,研究人员首次公开了通过人工设计的脱卤酶实现的光生物催化芳基卤化物的交叉偶联。该人工酶含一个基因编码的二苯甲酮生色团和一个定点修饰、距离可调的合成NiII(bpy)辅因子,以简化双催化过程。瞬时吸收研究提示在初级金属有机事件中可能存在能量转移活化。该设计策略有望大大扩展用于实用化有机合成的人工光酶库。
据了解,引导人工光酶催化非生物的成键反应具有很高的合成学价值,但挑战也很大。
附:英文原文
Title: Biocatalytic Cross-Coupling of Aryl Halides with a Genetically Engineered Photosensitizer Artificial Dehalogenase
Author: Yu Fu, Jian Huang, Yuzhou Wu, Xiaohong Liu, Fangrui Zhong, Jiangyun Wang
Issue&Volume: January 7, 2021
Abstract: Devising artificial photoenzymes for abiological bond-forming reactions is of high synthetic value but also a tremendous challenge. Disclosed herein is the first photobiocatalytic cross-coupling of aryl halides enabled by a designer artificial dehalogenase, which features a genetically encoded benzophenone chromophore and site-specifically modified synthetic NiII(bpy) cofactor with tunable proximity to streamline the dual catalysis. Transient absorption studies suggest the likelihood of energy transfer activation in the elementary organometallic event. This design strategy is viable to significantly expand the catalytic repertoire of artificial photoenzymes for useful organic transformations.
DOI: 10.1021/jacs.0c10882
Source: https://pubs.acs.org/doi/10.1021/jacs.0c10882
JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:14.612
官方网址:https://pubs.acs.org/journal/jacsat
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