Theoretical insight into the activity and selectivity in palladium/Ming-Phos-catalyzed three-component asymmetric synthesis of gem-diarylmethine silanes  

作　　者：Bo Xiao Tian-Yu Sun Junliang Zhang Yun-Dong Wu 

机构地区：[1]State Key Laboratory of Chemical Oncogenomics,Key Laboratory of Computational Chemistry and Drug Design,School of Chemical Biology and Biotechnology,Peking University Shenzhen Graduate School,Shenzhen 518055,China [2]Institute of Chemical Biology,Shenzhen Bay Laboratory,Shenzhen 518132,China [3]Department of Chemistry,Fudan University,Shanghai 200438,China [4]College of Chemistry and Molecular Engineering,Peking University,Beijing 100871,China

出　　处：《Science China Chemistry》2023年第10期2817-2827,共11页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21933004);the Key-Area Research and Development Program of Guangdong Province(2020B010188001,2020B0101350001);the Shenzhen Fundamental Research Program(GXWD20201231165807007-20200812124825001);the Shenzhen Bay Laboratory Supercomputing Center。

摘　　要：Recently,a three-component coupling reaction for efficient construction of gem-diarylmethine silanes was developed,utilizing a Pd-Ming-Phos catalyst.To explore the underlying mechanism governing this intriguing reaction,we have conducted comprehensive density functional theory(DFT)computations(M06-L/SDD/6-311++G(d,p)/SMD//B3LYP-D3/lanl2dz/6-31G(d,p)).DFT calculations reveal that the oxidative addition of Ar Br to Pd(0)is the rate-determining step,and the carbenation process of Ph CHN_(2)to Pd(Ⅱ)is the enantioselectivity-determining step.Moreover,the Ming-Phos ligand exhibits a self-adaptive nature,allowing it to dynamically adapt its coordination patterns with the metal center in different elementary steps,thereby enhancing the overall reactivity.The enantioselectivity is determined by both the trans effect and the side-arm effect of the ligand.This mechanism nicely explains why TY-Phos with P-tBu_(2)instead of the Ming-Phos with P-Ph2results in poor reactivity and much reduced enantioselectivity.This study not only provides deeper insights into the functioning principles of Sad Phos ligands but also offers valuable guidance for future ligand modifications and optimizations.

关 键 词：self-adaptive effect side-arm effect Ming-Phos ligand gem-diarylmethine silanes DFT study 

分 类 号：O621.251[理学—有机化学]