Construction of C-B axial chirality via dynamic kinetic asymmetric cross-coupling mediated by tetracoordinate boron

Yang，Kai1; Mao，Yanfei1; Zhang，Zhihan2; Xu，Jie1; Wang，Hao1; He，Yong1; Yu，Peiyuan2; Song，Qiuling1,3

2023-12-01

10.1038/s41467-023-40164-6

Nature Communications   Impact Factor & Quartile

2041-1723

Catalytic dynamic kinetic asymmetric transformation (DyKAT) provides a powerful tool to access chiral stereoisomers from racemic substrates. Such transformation has been widely employed on the construction of central chirality, however, the application in axial chirality remains underexplored because its equilibrium of substrate enantiomers is limited to five-membered metalacyclic intermediate. Here we report a tetracoordinate boron-directed dynamic kinetic asymmetric cross-coupling of racemic, configurationally stable 3-bromo-2,1-azaborines with boronic acid derivatives. A series of challenging C-B axially chiral compounds were prepared with generally good to excellent enantioselectivities. Moreover, this transformation can also be extended to prepare atropisomers bearing adjacent C-B and C-C diaxes with excellent diastereo- and enantio-control. The key to the success relies on the rational design of a reversible tetracoordinate boron intermediate, which is supported by theoretical calculations that dramatically reduces the rotational barrier of the original C-B axis and achieves the goal of DyKAT.

SCI

English

NI Journal Papers ; NI论文

Corresponding

Natural Science Foundation of Fujian Province[2022J02009];National Natural Science Foundation of China-Yunnan Joint Fund[21931013];

Science & Technology - Other Topics

Multidisciplinary Sciences

WOS:001036000300009

NATURE PORTFOLIO

2-s2.0-85165584610

Scopus

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.School of Chemistry and Chemical Engineering,Henan Normal University,Xinxiang,Henan,453007,China

Yang，Kai,Mao，Yanfei,Zhang，Zhihan,et al. Construction of C-B axial chirality via dynamic kinetic asymmetric cross-coupling mediated by tetracoordinate boron[J]. Nature Communications,2023,14(1).

Yang，Kai.,Mao，Yanfei.,Zhang，Zhihan.,Xu，Jie.,Wang，Hao.,...&Song，Qiuling.(2023).Construction of C-B axial chirality via dynamic kinetic asymmetric cross-coupling mediated by tetracoordinate boron.Nature Communications,14(1).

Yang，Kai,et al."Construction of C-B axial chirality via dynamic kinetic asymmetric cross-coupling mediated by tetracoordinate boron".Nature Communications 14.1(2023).