Direct visible-light-excited flavoproteins for redox-neutral asymmetric radical hydroarylation

doi:10.1038/s41929-023-01024-0

	Direct visible-light-excited flavoproteins for redox-neutral asymmetric radical hydroarylation
	Zhao, Beibei 5; Feng, Jianqiang 3,4; Yu, Lu 2; Xing, Zhongqiu 5; Chen, Bin 5; Liu, Aokun 2; Liu, Fulu 5; Shi, Fengming 5; Zhao, Yue 5; Tian, Changlin 1,2
刊名	NATURE CATALYSIS
	2023-09-14
ISSN号	2520-1158
DOI	10.1038/s41929-023-01024-0
通讯作者	Tian, Changlin(cltian@ustc.edu.cn) ; Wang, Binju(wangbinju2018@xmu.edu.cn) ; Huang, Xiaoqiang(huangx513@nju.edu.cn)
英文摘要	State-of-the-art non-natural photoenzymatic catalysis typically relies on either ultraviolet light activation or the formation of electron donor-acceptor complexes. Inspired by nature, herein we develop a biocatalytic scheme based on direct visible-light excitation of flavoprotein to achieve stereocontrolled intermolecular radical hydroarylation of alkenes with electron-rich arenes. Following visible-light activation, flavin-dependent ene-reductases-which naturally catalyse the two-electron reduction of activated alkenes-are repurposed to trigger single-electron oxidation of arenes and afford C(sp2)-C(sp3) bond-forming products in a redox-neutral and enantiodivergent fashion while both enantiomers are obtained with different enzymes. Experiments and computational simulations demonstrate that the reaction is initiated from the single-electron oxidation of substrate by the direct visible-light-excited flavoprotein, and explain the origin of enantioselectivity in this radical hydroarylation that is otherwise notoriously challenging to achieve by chemocatalysis. This work expands the repertoire of photoenzymatic catalysis and will stimulate the development of further biotransformations. Non-natural photobiocatalysis is attractive but usually involves UV light activation or the formation of electron donor-acceptor complexes. Now direct visible-light excitation of flavin-dependent ene-reductases allows stereocontrolled intermolecular radical hydroarylation of alkenes initiated by single-electron oxidation.
资助项目	National Key Research and Development Program of China[2022YFA0913000] ; National Key Research and Development Program of China[2019YFA0405600] ; National Key Research and Development Program of China[2019YFA0706900] ; National Natural Science Foundation of China[22277053] ; National Natural Science Foundation of China[22121001] ; National Natural Science Foundation of China[21927814] ; National Natural Science Foundation of China[21825703] ; Natural Science Foundation of Jiangsu Province[BK20220760] ; Youth Innovation Promotion Association CAS[2022455]
WOS关键词	EVOLUTION ; ENZYMES ; ACIDS
WOS研究方向	Chemistry
语种	英语
出版者	NATURE PORTFOLIO
WOS记录号	WOS:001067049000002
资助机构	National Key Research and Development Program of China ; National Natural Science Foundation of China ; Natural Science Foundation of Jiangsu Province ; Youth Innovation Promotion Association CAS
内容类型	期刊论文
源URL	[http://ir.hfcas.ac.cn:8080/handle/334002/132477]
专题	中国科学院合肥物质科学研究院
通讯作者	Tian, Changlin; Wang, Binju; Huang, Xiaoqiang
作者单位	1.Univ Sci & Technol China, Affiliated Hosp USTC 1, Div Life Sci & Med, Ctr Bioanalyt Chem,Hefei Natl Lab Phys Sci Microsc, Hefei, Peoples R China 2.Chinese Acad Sci, High Magnet Field Lab, Hefei, Peoples R China 3.Xiamen Univ, Coll Chem & Chem Engn, Fujian Prov Key Lab Theoret & Computat Chem, Xiamen, Peoples R China 4.Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen, Peoples R China 5.Nanjing Univ, Chem & Biomed Innovat Ctr, Sch Chem & Chem Engn, State Key Lab Coordinat Chem, Nanjing, Peoples R China
推荐引用方式 GB/T 7714	Zhao, Beibei,Feng, Jianqiang,Yu, Lu,et al. Direct visible-light-excited flavoproteins for redox-neutral asymmetric radical hydroarylation[J]. NATURE CATALYSIS,2023.
APA	Zhao, Beibei.,Feng, Jianqiang.,Yu, Lu.,Xing, Zhongqiu.,Chen, Bin.,...&Huang, Xiaoqiang.(2023).Direct visible-light-excited flavoproteins for redox-neutral asymmetric radical hydroarylation.NATURE CATALYSIS.
MLA	Zhao, Beibei,et al."Direct visible-light-excited flavoproteins for redox-neutral asymmetric radical hydroarylation".NATURE CATALYSIS (2023).