Issue 16, 2017

Mechanistic insight into the regioselectivity of Pd(ii)-catalyzed C–H functionalization of N-methoxy cinnamamide

Abstract

Computational studies have been applied to gain insight into the mechanism of Pd(II) catalyzed α-C–H functionalization of N-methoxy cinnamamide. The results show that the whole catalytic cycle proceeds via sequential six steps, including (i) catalyst Pd(t-BuNC)2 oxidation with O2, (ii) O–H deprotonation, (iii) t-BuNC migratory insertion to the Pd–C bond, (iv) acyl migration, (v) C–H activation and (vi) reductive elimination. The regioselectivity for different C–H activation sites depends on the coordination structures of α-C or β-C to the palladium(II) center. The coordination of α-C to the palladium(II) center shows a regular planar quadrilateral structure, which is stable. However, the β-C coordinating to the palladium(II) center mainly exhibits a distorted quadrilateral structure, which is relatively unstable. Thus, the barrier of α-C–H activation is much lower than that of β-C–H activation. The present results provide a deep understanding of the site-selectivity of C–H activation.

Graphical abstract: Mechanistic insight into the regioselectivity of Pd(ii)-catalyzed C–H functionalization of N-methoxy cinnamamide

Supplementary files

Article information

Article type
Paper
Submitted
14 Feb 2017
Accepted
22 Mar 2017
First published
23 Mar 2017

Dalton Trans., 2017,46, 5288-5296

Mechanistic insight into the regioselectivity of Pd(II)-catalyzed C–H functionalization of N-methoxy cinnamamide

W. Fan, C. Sun, F. Huang, J. Liu, X. Zhao, X. Sheng and D. Chen, Dalton Trans., 2017, 46, 5288 DOI: 10.1039/C7DT00547D

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