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

doi:10.1002/poc.3902

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 Publication › Article › peer-review

5 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 language	English
Article number	e3902
Journal	Journal of Physical Organic Chemistry
Volume	32
Issue number	2
DOIs	https://doi.org/10.1002/poc.3902
Publication status	Published - Feb 2019
Externally published	Yes

Keywords

DFT
QTAIM
combined Lewis acid
mechanism

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry

Access to Document

10.1002/poc.3902

Cite this

Liu, C., Sang, S., Chen, F., Yan, Y., Zhang, C., & Huang, W. (2019). Me ₃ SiBr/InCl ₃ catalyzed allylation of alcohols: Identifying the combined Lewis structure and investigating the reaction mechanism. Journal of Physical Organic Chemistry, 32(2), Article e3902. https://doi.org/10.1002/poc.3902

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

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.",

keywords = "DFT, QTAIM, combined Lewis acid, mechanism",

author = "Changmei Liu and Shenglong Sang and Fei Chen and Yan Yan and Cong Zhang and Wei Huang",

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year = "2019",

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doi = "10.1002/poc.3902",

language = "English",

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Liu, C, Sang, S, Chen, F, Yan, Y, Zhang, C & Huang, W 2019, 'Me ₃ SiBr/InCl ₃ catalyzed allylation of alcohols: Identifying the combined Lewis structure and investigating the reaction mechanism', Journal of Physical Organic Chemistry, vol. 32, no. 2, e3902. https://doi.org/10.1002/poc.3902

Me ₃ SiBr/InCl ₃ catalyzed allylation of alcohols: Identifying the combined Lewis structure and investigating the reaction mechanism. / Liu, Changmei; Sang, Shenglong; Chen, Fei et al.
In: Journal of Physical Organic Chemistry, Vol. 32, No. 2, e3902, 02.2019.

Research output: Journal Publication › Article › peer-review

TY - JOUR

T1 - Me 3 SiBr/InCl 3 catalyzed allylation of alcohols

T2 - Identifying the combined Lewis structure and investigating the reaction mechanism

AU - Liu, Changmei

AU - Sang, Shenglong

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AU - Yan, Yan

AU - Zhang, Cong

AU - Huang, Wei

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N2 - 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.

AB - 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.

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