Construction of C-B Axial Chirality Via Dynamic Kinetic Asymmetric Cross-coupling Mediated by Tetracoordinate Boron

Overview

Journal Nat Commun

Specialty Biology

Date 2023 Jul 24

PMID 37488114

Authors

Kai Yang

Yanfei Mao

Zhihan Zhang

Jie Xu

Hao Wang

Yong He

Peiyuan Yu

Qiuling Song

Affiliations

Soon will be listed here.

Abstract

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.

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