Enhanced Sampling Simulations on Transition-Metal-Catalyzed Organic Reactions:Zirconocene-Catalyzed Propylene Polymerization and Sharpless Epoxidation  

作　　者：Xu Han Tian-Yu Sun Yi Isaac Yang Jun Zhang Jing Qiu Zhaoping Xiong Nan Qiao Yun-Dong Wu Yi Qin Gao 

机构地区：[1]Institute of Theoretical and Computational Chemistry,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871 [2]Shenzhen Bay Laboratory,Shenzhen 518132 [3]Changping Laboratory,Beijing 102200 [4]Laboratory of Health Intelligence,Huawei Cloud Computing Technologies Co.,Ltd.,Guizhou 550025

出　　处：《CCS Chemistry》2024年第4期964-975,共12页中国化学会会刊（英文）

基　　金：supported by National Natural Science Foundation of China(grant nos.21927901,21821004,and 21873007 to Y.Q.G.,grant no.21933004 to Y.D.W.,grant nos.22273061 and 22003042 to Y.I.Y.);the Key-Area Research and Development Program of Guangdong Province(grant no.2020B0101350001 to Y.D.W.).

摘　　要：The bond breaking and forming in chemical reactions is a typical rare event,which is one of the difficult problems in molecular dynamics simulations.Numerous enhanced sampling methods have been developed to extend the time scale covered by molecular simulations.However,the difficulties of obtaining appropriate collective variables from complicated reaction pathways and a controlled sampling over the desired phase space remain as challenges.Herein,we use MetaITS,which combines metadynamics and integrated tempered sampling,to increase the sampling efficiency for chemical reactions.Metadynamics with collective variables obtained by harmonic linear discriminant analysis can efficiently decrease the main energy barrier of chemical reaction.Meanwhile,integrated tempered sampling can enhance the exploration of other degrees of freedom.In this study,we applied the MetaITS method to two transition-metal-catalyzed organic reactions with complicated reaction coordinates.We simulated here a zirconocene-catalyzed propylene polymerization to investigate the regioselectivity and temperature effects.We also studied a Sharpless epoxidation reaction,for which both chiral products are observed through simulation.

关 键 词：molecular dynamics enhanced sampling METADYNAMICS integrated tempering sampling propylene polymerization Sharpless epoxidation 

分 类 号：O62[理学—有机化学]