A Photoenzymatic Strategy for Radical-Mediated Stereoselective Hydroalkylation with Diazo Compounds

被引：31

作者：

Duan, Xinyu ^{[1
]}

Cui, Dong ^{[1
]}

Wang, Zhiguo ^{[3
]}

Zheng, Dannan ^{[1
]}

Jiang, Linye ^{[1
]}

Huang, Wen-Yu ^{[2
]}

Jia, Yi-Xia ^{[2
,4
]}

Xu, Jian ^{[1
]}

机构：

[1] Zhejiang Univ Technol, Coll Biotechnol & Bioengn, Hangzhou 310014, Peoples R China

[2] Zhejiang Univ Technol, Coll Chem Engn, Hangzhou 310014, Peoples R China

[3] Hangzhou Normal Univ, Inst Aging Res, Sch Basic Med Sci, Hangzhou 311121, Peoples R China

[4] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 05期

基金：

中国国家自然科学基金;

关键词：

Diazo Compounds; Hydroalkylation; Photo-Biocatalysis; Radicals; DIRECTED EVOLUTION; DEPENDENT ENZYMES; CYCLOPROPANATION; BIOCATALYSIS; CYCLIZATION; CHEMISTRY;

D O I：

10.1002/anie.202214135

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Carbene insertion reactions initiated with diazo compounds have been widely used to develop unnatural enzymatic reactions. However, alternative functionalization of diazo compounds in enzymatic processes has been unexploited. Herein, we describe a photoenzymatic strategy for radical-mediated stereoselective hydroalkylation with diazo compounds. This method generates carbon-centered radicals through an ene reductase catalyzed photoinduced electron transfer process from diazo compounds, enabling the synthesis of gamma-stereogenic carbonyl compounds in good yields and stereoselectivities. This study further expands the possible reaction patterns in photo-biocatalysis and offers a new approach to solving the selectivity challenges of radical-mediated reactions.

引用

页数：6

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