Issue 3, 2017

Mechanism of selective C–H cyanation of 2-phenylpyridine with benzyl nitrile catalyzed by CuBr: a DFT investigation

Abstract

The mechanism of selective C–H cyanation of 2-phenylpyridine catalyzed by CuBr was investigated using the DFT method at the B3LYP/6-31+G(d,p) level, and the integral equation formalism polarized continuum model (IEFPCM) was applied to simulate the solvent effect. The computational results suggested that 2-phenylacetonitrile can convert into benzoyl cyanide under O2 conditions via two paths (a and b), and also, 2-phenylacetonitrile can first react with the O2 anion to yield 2-hydroxy-2-phenylacetonitrile, and then 2-hydroxy-2-phenylacetonitrile goes through oxidative dehydrogenation to yield benzoyl cyanide via four different paths (c, d, e and f). The other part reaction of the conversion of 2-phenylpyridine to 2-(pyridin-2-yl)-benzonitrile catalyzed by CuBr can go through three paths (g, h and i) which involve the coordination of CN and the N atom of 2-phenylpyridine with Cu cations, and then the processes of addition and oxydehydrogenation reactions lead to the final product 2-(pyridin-2-yl)benzonitrile. In addition, another path (j) without the participation of CuBr could also occur. The results could provide valuable insights into these types of interactions and related ones.

Graphical abstract: Mechanism of selective C–H cyanation of 2-phenylpyridine with benzyl nitrile catalyzed by CuBr: a DFT investigation

Supplementary files

Article information

Article type
Research Article
Submitted
23 अक्तूबर 2016
Accepted
09 दिसम्बर 2016
First published
12 दिसम्बर 2016

Org. Chem. Front., 2017,4, 377-385

Mechanism of selective C–H cyanation of 2-phenylpyridine with benzyl nitrile catalyzed by CuBr: a DFT investigation

D. Zhou, F. Yang, X. Yang, C. Yan, P. Zhou and H. Jing, Org. Chem. Front., 2017, 4, 377 DOI: 10.1039/C6QO00652C

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.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements