Zheqi Li, Hongjin Shi, Xueying Chen, Long Peng, Yuqiang. Li* and Guoyin Yin*.J. Am. Chem. Soc.（阴国印、李玉强）

Abstract：

        Chiral boronic esters are a class of versatile building blocks. We describe herein an asymmetric nickel-catalyzed borylative coupling of terminal alkenes with nonactivated alkyl halides. The success of this asymmetric reaction is ascribed to the application of a chiral anionic bisoxazoline ligand. This study provides a three-component strategy to access α- and β-stereogenic boronic esters from easily accessible starting materials. This protocol is characterized by mild reaction conditions, wide substrate scope and high regio- and enantioselectivity. We also showcase the value of this method in simplifying the synthesis of several drug molecules. Mechanistic studies suggest that the generation of enantioenriched boronic esters bearing an α-stereogenic center results from a stereoconvergent process, while the enantioselectivity-controlling step in the generation of boronic esters with a β-stereocenter is switched to the olefin migratory insertion step due to coordination of an ester group.

        论文链接：https://pubs.acs.org/doi/10.1021/jacs.3c01040