Neutral Monodentate and Hypervalent Chalcogen Bond Catalysis on the Intramolecular Rauhut-Currier Reaction of Bis(enones): A DFT Study.

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.