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Palladium-mediated CO2 extrusion followed by insertion of isocyanates for the synthesis of benzamides: translating fundamental mechanistic studies to develop a catalytic protocol

Citation

Yang, Y and Canty, AJ and McKay, AI and Donnelly, PS and O'Hair, RAJ, Palladium-mediated CO2 extrusion followed by insertion of isocyanates for the synthesis of benzamides: translating fundamental mechanistic studies to develop a catalytic protocol, Organometallics, 39, (3) pp. 453-467. ISSN 0276-7333 (2020) [Refereed Article]

Copyright Statement

© 2020 American Chemical Society

DOI: doi:10.1021/acs.organomet.9b00820

Abstract

Mechanistic studies of a stoichiometric palladium-mediated ExIn (ExIn = extrusion–insertion) decarboxylative amidation of aromatic carboxylic acids are presented, providing gas-phase and condensed-phase spectroscopic data, as well as theoretical computational evidence for intermediates in a proposed stepwise process. The understanding gained from these mechanistic studies directed the development of a palladium-catalyzed procedure in which benzamides are obtained in good to high yields in a one-pot 30 min microwave irradiation assisted protocol. A combination of experimental data and DFT calculations reveals that certain ligand additives favor the selective formation of benzamides rather than the undesired protodecarboxylation side product.

Item Details

Item Type:Refereed Article
Keywords:palladium catalysis, DFT, mass spectrometry, reaction mechanism, organic synthesis
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:137421
Year Published:2020
Web of Science® Times Cited:7
Deposited By:Chemistry
Deposited On:2020-02-12
Last Modified:2021-07-05
Downloads:0

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