黄素组
立体中心
烯烃
分子间力
化学
活动站点
电子转移
光激发
高价分子
催化作用
对苯二酚
光化学
组合化学
立体化学
有机化学
对映选择合成
酶
试剂
分子
激发态
核物理学
物理
作者
Claire Page,Simon Cooper,Jacob DeHovitz,Daniel G. Oblinsky,Kyle Biegasiewicz,Alyssa H. Antropow,Kurt W. Armbrust,Michael Ellis,Lawrence G. Hamann,Evan Horn,Kevin Oberg,Gregory D. Scholes,Todd K. Hyster
标识
DOI:10.26434/chemrxiv.13173596
摘要
Intermolecular C–C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent ‘ene’reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, 𝛼-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. This active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.
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