Construction of boron-stereogenic compounds via enantioselective Cu-catalyzed desymmetric B-H bond insertion reaction

Guan Zhang; Zhihan Zhang; Mengyuan Hou; Xinping Cai; Kai Yang; Peiyuan Yu; Qiuling Song

doi:10.1038/s41467-022-30287-7

Construction of boron-stereogenic compounds via enantioselective Cu-catalyzed desymmetric B-H bond insertion reaction

Nat Commun. 2022 May 12;13(1):2624. doi: 10.1038/s41467-022-30287-7.

Authors

Guan Zhang^#¹, Zhihan Zhang^#², Mengyuan Hou¹, Xinping Cai¹, Kai Yang¹, Peiyuan Yu³, Qiuling Song^{4

5

6

7}

Affiliations

¹ Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian, 350108, China.
² Department of Chemistry and Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, China.
³ Department of Chemistry and Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, China. yupy@sustech.edu.cn.
⁴ Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian, 350108, China. qsong@hqu.edu.cn.
⁵ Department of Chemistry and Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, China. qsong@hqu.edu.cn.
⁶ Institute of Next Generation Matter Transformation, College of Materials Science Engineering at Huaqiao University 668 Jimei Boulevard, Xiamen, Fujian, 361021, China. qsong@hqu.edu.cn.
⁷ School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007, China. qsong@hqu.edu.cn.

^# Contributed equally.

Abstract

Compared with the well-developed carbon-stereogenic chemistry, the construction of boron-stereogenic compounds remains undeveloped and challenging. Herein, the previously elusive catalytic enantioselective construction of boron-stereogenic compounds has been achieved through enantioselective desymmetric B-H bond insertion reaction. The B-H bond insertion reaction of 2-arylpyridine-boranes with versatile diazo compounds under chiral copper catalyst can afford boron-stereogenic compounds with good to excellent enantioselectivity. Moreover, the synthetic utility of this reaction is demonstrated by the scalability and downstream transformations. DFT calculations provide insights into the reaction mechanism and the origin of stereoselectivity.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Boron Compounds* / chemistry
Boron*
Catalysis
Copper / chemistry
Stereoisomerism

Substances

Boron Compounds
Copper
Boron