Wang Zhuo, Zhao Chang, Li Xiaoyan, Shi Bo, Zeng Yanli
College of Chemistry and Materials Science, Hebei Key Laboratory of Inorganic Nano-materials, Hebei Normal University, Shijiazhuang, 050024, P. R. China.
National Experimental Chemistry Teaching Center, Hebei Normal University, Shijiazhuang, 050024, P. R. China.
Chemistry. 2023 May 2;29(25):e202300171. doi: 10.1002/chem.202300171. Epub 2023 Mar 17.
Recently, the green and high efficient of chalcogen bond (ChB) catalysis has been aroused great interest. In this work, the ChB catalysis has been applied to the intramolecular Rauhut-Currier (RC) reaction of bis(enones). The mechanism was divided into four processes: the promoter addition process, the carbon-carbon bond coupling process, the hydrogen transfer process, and the promoter elimination process. This study shows that the ChB catalyst could act on the promoter and reactant in the RC reaction, respectively. And the path 2 of ChB catalyst direct acting on the reactant is considered to be a relatively favorable channel of the reaction due to a lower energy barrier. In addition, all six catalysts could achieve good catalytic effect. Analysis of the properties shows that the formation of chalcogen bond mainly promotes the charge transfer of LP(O)-BD*(C-Se) in the carbon-carbon bond formation (key step), so that the charge of C(4) atom become more positive, thereby accelerating the reaction.
最近，硫族元素键（ChB）催化的绿色高效性引起了极大的兴趣。在这项工作中，ChB催化已应用于双烯酮的分子内劳胡特-柯里尔（RC）反应。其机理分为四个过程：促进剂加成过程、碳-碳键偶联过程、氢转移过程和促进剂消除过程。该研究表明，ChB催化剂可分别作用于RC反应中的促进剂和反应物。并且，由于能量垒较低，ChB催化剂直接作用于反应物的路径2被认为是该反应相对有利的通道。此外，所有六种催化剂都能实现良好的催化效果。性质分析表明，硫族元素键的形成主要促进了碳-碳键形成（关键步骤）中LP(O)-BD*(C-Se)的电荷转移，使C(4)原子的电荷更正，从而加速了反应。
