Me3SiBr/InCl3 catalyzed allylation of alcohols: Identifying the combined Lewis structure and investigating the reaction mechanism. (26th October 2018)

• Record Type: Journal Article
• Authors: Liu, Changmei; Sang, Shenglong; Chen, Fei; Yan, Yan; Zhang, Cong; Huang, Wei
• Is Part Of: Journal of physical organic chemistry. Volume 32:Number 2(2019)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-10-26
• Subjects: combined Lewis acid -- DFT -- mechanism -- QTAIM; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3902
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract: The combined Lewis acid Me3 SiBr/InCl3 shows unique performance in multireactions. The topology and catalytic properties of Me3 SiBr/InCl3 were investigated by DFT method for clarifying the nature of chemical bonds and interactions. Quantum theory of atoms in molecules (QTAIM) analysis showed that the interaction between Me3 Si‐halide and In‐trihalide mainly belongs to the closed‐shell interaction. Natural bond order of Br─In is 0.610 in INT_0 while natural bond order of Cl─In in INT_1 is only 0.081 at SMD‐ωB97XD/def2‐SVP level. The coupling reaction mechanism of alcohol and allyltrimethylsilane catalyzed by the complex of Me3 SiBr/InCl3 was investigated with DFT method. The combined Lewis acid activates the hydroxyl group by strong coordination to silicone center, which leads to the generation of carbocation. Me3 Si + moiety from the combined Lewis acid is consumed and converts into the side product Me3 SiOSiMe3 . Furthermore, the reactant allyltrimethylsilane is introduced into the system to bring out the final product, and the complex Me3 SiBr/InCl3 is reproduced at the same time. The combined Lewis acid Me3 SiBr/InCl3 not only works as the catalyst for the reaction but also involves in the generation of side product. Abstract : The interaction between two moieties of combined Lewis acid Me3SiBr/InCl3 is mainly ionic interaction. In coupling reaction of alcohol and allyltrimethylsilane, the combined Lewis acid Me3SiBr/InCl3 not only works as the catalyst for the reaction but also involves in the generation of side product.