MP2 study on the selectivity of gold catalysis with alkenes and furan activation

초록

Gold-catalyzed strategies for inactivated multiple bond system to construct the C-C bond have been attracted a lot of attention. Mechanisms of hydroarylation of α,β-unsaturated alkenes by furan with AuCl3 catalyst were investigated with MP2 method. The results shed light on the mechanism previously suggested by experiments. Calculations show that the direct auration of the conjugated furan system by AuCl3 is favoured among three possible pathways. Due to the electron rich nature of the furan ring, the electron donation from furan to the vacant orbitals of Au to form the stable C-Au σ-bond largely enhances the electrophilicity of the conjugated furan ring. In the reaction paths, hydrogen bonds play important roles in stabilizing the intermediates. The hydrogen transfer to form the final product is a very important step in the reaction. Compared with the reaction without catalyst, the role of the catalyst AuCl3 is to assist the hydrogen transfer and largely lower the energy barriers in the preferred reaction mechanism.