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 

机构地区：[1]College of Chemistry and Material Science,Shandong Agricultural University,Taian,271018,P.R.China

出　　处：《Chemical Research in Chinese Universities》2023年第2期276-282,共7页高等学校化学研究（英文版）

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.

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 functional.The reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—Cσbonds.After the coordination/insertion of alkenes,respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of CptBuRh.The 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 elimination.The stereoselective transfer and ring rotation are specific for benzoquinone and cyclopropenone.The 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.

关 键 词：ANNULATION Activated alkene TRANSMETALATION Coordination/insertion M06-2X functional 

分 类 号：O621.251[理学—有机化学]