Theoretical Investigation of the Mechanism of Rh(III)-catalyzed Annulation of 2-Biphenylboronic Acid with Activated Alkene |
| |
Authors: | LU Nan MIAO Chengxia LAN Xiaozheng |
| |
Affiliation: | College of Chemistry and Material Science, Shandong Agricultural University, Taian 271018, P. R. China |
| |
Abstract: | The mechanism is investigated for CptBuRh(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—C σ bonds. 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 CptBuRh(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. |
| |
Keywords: | Annulation Activated alkene Transmetalation Coordination/insertion M06-2X functional |
|
| 点击此处可从《高等学校化学研究》浏览原始摘要信息 |
|
点击此处可从《高等学校化学研究》下载全文 |