Theoretical Investigation of the Mechanism of Rh(III)-catalyzed Annulation of 2-Biphenylboronic Acid with Activated Alkene

作     者：LU Nan MIAO Chengxia LAN Xiaozheng LU Nan;MIAO Chengxia;LAN Xiaozheng

作者机构：College of Chemistry and Material ScienceShandong Agricultural UniversityTaian271018P.R.China 

出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)

年 卷 期：2023年第39卷第2期

页      面：276-282页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：National Natural Science Foundation of China(Nos.21973056,21972079) Natural Science Foundation of Shandong Province,China(No.ZR2019MB050) Project of the Key Laboratory of Agricultural Film Application of Ministry of Agriculture and Rural Affairs,China 

主　　题：Annulation Activated alkene Transmetalation Coordination/insertion M06-2X functional 

摘      要：The mechanism is investigated for Cp^(tBu)Rh(OH)_(2)-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X *** reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—Cσ*** the coordination/insertion of alkenes,respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of *** promotion of Cp^(tBu)Rh(OH)_(2) lies in the barrier decrease of transmetalation and C-H activation ready for coordination/insertion ensuring the smooth progress of common rate-limiting reductive *** stereoselective transfer and ring rotation are specific for benzoquinone and *** role of Rh(III)catalyst and release of Rh(I)is supported by Multiwfn analysis on frontier molecular orbital(FMO)of specific transiton states(TSs)and Mayer bond order(MBO)value of vital bonding,breaking.