Me 3 SiBr/InCl 3 catalyzed allylation of alcohols: Identifying the combined Lewis structure and investigating the reaction mechanism

Changmei Liu, Shenglong Sang, Fei Chen, Yan Yan, Cong Zhang, Wei Huang

Research output: Journal PublicationArticlepeer-review

3 Citations (Scopus)

Abstract

The combined Lewis acid Me 3 SiBr/InCl 3 shows unique performance in multireactions. The topology and catalytic properties of Me 3 SiBr/InCl 3 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 Me 3 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 Me 3 SiBr/InCl 3 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. Me 3 Si + moiety from the combined Lewis acid is consumed and converts into the side product Me 3 SiOSiMe 3 . Furthermore, the reactant allyltrimethylsilane is introduced into the system to bring out the final product, and the complex Me 3 SiBr/InCl 3 is reproduced at the same time. The combined Lewis acid Me 3 SiBr/InCl 3 not only works as the catalyst for the reaction but also involves in the generation of side product.

Original languageEnglish
Article numbere3902
JournalJournal of Physical Organic Chemistry
Volume32
Issue number2
DOIs
Publication statusPublished - Feb 2019
Externally publishedYes

Keywords

  • DFT
  • QTAIM
  • combined Lewis acid
  • mechanism

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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