Diversity-oriented synthesis of P-stereogenic and axially chiral monodentate biaryl phosphines enabled by C-P bond cleavage
Liangzhi Pang, Zhan Huang, Qilin Sun, Gen Li, Jiaojiao Liu, Baoli Li, Congyue Ma, Jiaxu Guo, Chuan‐Zhi Yao, Jie Yu, Qiankun Li
Abstract
Abstract Chiral monodentate biaryl phosphines (MOPs) have attracted intense attention as chiral ligands over the past decades. However, the creation of structurally diverse chiral MOPs with both P - and axial chirality is still in high demand but challenging. Here, we show a distinct strategy for diversity-oriented synthesis of structurally diverse MOPs containing both P - and axial chirality enabled by enantioselective C-P bond cleavage. The key chiral Pd II intermediates, generated through the stereoselective oxidative addition of C-P bond, could be trapped by alkynes, R 3 Si-Bpin, diboron esters or reduced by H 2 O/B 2 pin 2 , leading to enantioenriched structurally diverse MOPs in excellent diastereo- and enantioselectivities. Based on the outstanding properties of the parent scaffolds, the P - and axially chiral monodentate biaryl phosphines serve as excellent catalysts in asymmetric [3 + 2] annulation of MBH carbonate affording the chiral functionalized bicyclic imide.