化学
催化作用
光化学
黄素组
氢化物
光催化
烯类反应
氢原子
吡啶
组合化学
反应机理
立体选择性
烯烃
氢
酶
光催化
立体化学
药物化学
有机化学
烷基
作者
Yuji Nakano,Michael J. Black,Andrew J. Meichan,Braddock A. Sandoval,Megan M. Chung,Kyle F. Biegasiewicz,Tianyu Zhu,Todd K. Hyster
标识
DOI:10.1002/anie.202003125
摘要
Abstract Flavin‐dependent ‘ene’‐reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using the native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in the presence of a photoredox catalyst. Experimental evidence suggests the reaction proceeds via a radical mechanism where the vinyl pyridine is reduced to the corresponding neutral benzylic radical in solution. DFT calculations reveal this radical to be “dynamically stable”, suggesting it is sufficiently long‐lived to diffuse into the enzyme active site for stereoselective hydrogen atom transfer. This reduction mechanism is distinct from the native one, highlighting the opportunity to expand the synthetic capabilities of existing enzyme platforms by exploiting new mechanistic models.
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