He Jun, Zhang Jie, Li Yunhe, Han Yan-Bo, Li Mengyang, Zhao Xiang
Institute of Molecular Science and Applied Chemistry, School of Chemistry, State Key Laboratory of Electrical Insulation and Power Equipment & MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049, China.
School of Materials Science and Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China.
ACS Omega. 2023 Jun 15;8(25):22637-22645. doi: 10.1021/acsomega.3c01279. eCollection 2023 Jun 27.
The concept of diastereoselectivity switch in gold catalysis is investigated, which primarily depends on the effects of ligand and counterion. The origins of gold-catalyzed post-Ugi ipso-cyclization for the diastereoselective synthesis of spirocyclic pyrrol-2-one-dienone have been explored with density functional theory calculations. The reported mechanism emphasized the importance of the cooperation of ligand and counterion in diastereoselectivity switch, leading to the stereocontrolling transition states. Furthermore, the nonbonding interactions primarily between the catalyst and the substrate play a significant role in the cooperation of ligand and counterion. This work would be useful to further understand the reaction mechanism of gold-catalyzed cyclization and the effects of ligand and counterion.
研究了金催化中立体选择性开关的概念，其主要取决于配体和抗衡离子的影响。采用密度泛函理论计算方法，探索了金催化的Ugi反应后原位环化反应对螺环吡咯-2-酮-二烯酮进行非对映选择性合成的反应机理。报道的机理强调了配体和抗衡离子在立体选择性开关中的协同作用的重要性，从而导致立体控制的过渡态。此外，主要存在于催化剂和底物之间的非键相互作用在配体和抗衡离子的协同作用中起着重要作用。这项工作将有助于进一步理解金催化环化反应的机理以及配体和抗衡离子的影响。
