Visible-light-induced enantioselective radical cross-coupling of C(sp3)-borazirconocene

被引:4
|
作者
Yang, Chao [1 ]
Bai, Songlin [2 ]
Gao, Yadong [3 ]
Wu, Qingcui [1 ]
Qi, Xiangbing [1 ,4 ]
机构
[1] Natl Inst Biol Sci, 7 Sci Pk Rd,Zhongguancun Life Sci Pk, Beijing 102206, Peoples R China
[2] Tsinghua Univ, Sch Life Sci, Beijing 100084, Peoples R China
[3] Guangzhou Lab, Guangzhou 510320, Guangdong, Peoples R China
[4] Tsinghua Univ, Tsinghua Inst Multidisciplinary Biomed Res, Beijing 100084, Peoples R China
来源
CHEM | 2023年 / 9卷 / 08期
基金
中国国家自然科学基金;
关键词
SYNTHETIC APPLICATIONS; SUZUKI REACTIONS; NUCLEOPHILES; SECONDARY;
D O I
10.1016/j.chempr.2023.04.006
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Asymmetric cross-coupling involving sp3-hybridized carbon nucleophiles has become one of the most powerful methods for the synthesis of chiral C(sp3)-enriched three-dimensional (3D) structures, which are essential scaffolds for pharmaceuticals, agrochemicals, and functional materials. To date, in contrast to the application of several alkyl organometallic nucleophiles (e.g., alkyl-zinc, boron, and magnesium) in asymmetric cross-couplings, more easily accessible alkylzirconocene reagents have received much less attention. Herein, we report a visible-light-induced, Ni-catalyzed, asymmetric cross-coupling of gem-borazirconocene alkenes with aryl and unactivated alkyl halides, furnishing a diverse series of valuable chiral alkylboron compounds in good yield and with excellent enantioselectivity. Additionally, mechanistic investigations, including DFT calculations, radical trapping, and kinetic experiments, show how the inherent photoreactivity of alkyl-Zr controls the radical generation step that is essential for cross-coupling, unveiling an efficient means for highly stereoconvergent, gem-borazirconocene alkenebased, single-electron asymmetric transformations.
引用
收藏
页码:2222 / 2236
页数:16
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