eCite Digital Repository

Understanding the mechanism of CuI-catalyzed N-H carboxylation of heterocyclic rings with CO2 from a theoretical point of view

Citation

Batebi, H and Zarkoob, F and Daraei, K and Yates, BF and Ariafard, A, Understanding the mechanism of CuI-catalyzed N-H carboxylation of heterocyclic rings with CO2 from a theoretical point of view, Journal of Organometallic Chemistry, 748 pp. 89-97. ISSN 0022-328X (2013) [Refereed Article]

Copyright Statement

Copyright 2013 Elsevier B.V

DOI: doi:10.1016/j.jorganchem.2013.04.060

Abstract

The copper catalyzed carboxylation of heterocyclic rings has been studied with density functional theory. We find strong linear correlations between the pKa of the heterocycles and various steps in the reaction, including the initial copper-bound adduct and the barriers for NeH and CO2 activations. Using the mechanism proposed by Nolan, Cazin and coworkers, we find that the heterocycles fall into two groups (A and B) and we show that having a nitrogen atom adjacent to NeH in the ring (Group B) is important in lowering the barrier for the two key steps, that is, the NeH and CO2 activations. However our results for the heterocycles in Group A did not match up to the experimental results. In order to account fully for the observed experimental reactivity we have proposed an alternative mechanism involving promotion by base, i.e. the coordination of OH- to CuI before the N-H and CO2 activations to occur. This mechanism is the likely one to operate for Group A compounds, and is competitive with the mechanism proposed by Nolan and Cazin for Group B compounds.

Item Details

Item Type:Refereed Article
Keywords:CO2 activation, density functional theory, N-H deprotonation, N-H activation, copper complexes, carboxylation reaction
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Yates, BF (Professor Brian Yates)
Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:89240
Year Published:2013
Deposited By:Chemistry
Deposited On:2014-02-27
Last Modified:2015-02-05
Downloads:0

Repository Staff Only: item control page