A comparative DFT study of TBD-catalyzed reactions of amines with CO2 and hydrosilane: the effect of solvent polarity on the mechanistic preference and the origins of chemoselectivities

Chaoshen Zhang; Yu Lu; Ruihua Zhao; Wasihun Menberu; Jiandong Guo; Zhi-Xiang Wang

doi:10.1039/C8CC05788E

You do not have JavaScript enabled. Please enable JavaScript to access the full features of the site or access our non-JavaScript page.

A comparative DFT study of TBD-catalyzed reactions of amines with CO₂ and hydrosilane: the effect of solvent polarity on the mechanistic preference and the origins of chemoselectivities†

Chaoshen Zhang,^a Yu Lu,^a Ruihua Zhao,^a Wasihun Menberu,^a Jiandong Guo^a and Zhi-Xiang Wang

*^a

Author affiliations

* Corresponding authors

^a School of Chemical Sciences, University of Chinese Academy of Sciences, Jia #19, Yuquan Road, Beijing, China
E-mail: zxwang@ucas.ac.cn

Abstract

A DFT comparative mechanistic study unveils that the TBD-catalyzed reactions of amines with CO₂ and hydrosilanes may either undergo a neutral mechanism or a mechanism involving free ions, depending on the polarity of the solvent. The nucleophilicity of the amines is an important factor to determine the chemoselectivities of the reactions to give formamide or aminal/N-methylated amine.

Download options Please wait...

Supplementary files

Supplementary information PDF (1231K)

Article information

DOI: https://doi.org/10.1039/C8CC05788E
Article type: Communication
Submitted: 17 Jul 2018
Accepted: 31 Aug 2018
First published: 01 Sep 2018

Download Citation

Chem. Commun., 2018,54, 10870-10873

Permissions

Request permissions

A comparative DFT study of TBD-catalyzed reactions of amines with CO₂ and hydrosilane: the effect of solvent polarity on the mechanistic preference and the origins of chemoselectivities

C. Zhang, Y. Lu, R. Zhao, W. Menberu, J. Guo and Z. Wang, Chem. Commun., 2018, 54, 10870 DOI: 10.1039/C8CC05788E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Social activity

Fetching data from CrossRef.
This may take some time to load.

Chemical Communications