Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.



Mechanistic Details of the Cobalt-Mediated Dehydrogenative Dimerization of Aminoquinoline-Directed Benzamides

Abstract

Key mechanistic features of the cobalt-mediated and aminoquinoline-directed dehydrogenative aryl-aryl coupling were investigated computationally and experimentally. A series of CoII and CoIII complexes relevant to the proposed reaction cycle have been synthesized and characterized. Stoichiometric reactions and electrochemical studies were used to probe the role of different additives in the reaction pathway. Computationally, three different mechanisms, such as charge neutral, anionic, and dimetallic were explored. It is shown that the mono-metallic anionic and charge neutral mechanisms are the most favorable ones, among of which the former mechanism is slightly more encouraging and proceeds via the: (a) concerted-metalation-deprotonation (CMD) of the first benzamide C–H bond, (b) PivOH-to-PivO- rearrangement, (c) CMD of the second benzamide C–H bond, (d) C-C coupling, (e) product formation facilitated by the amide nitrogen re-protonation, and (f) catalyst regeneration. The rate-determining step of this multi-step process is the C–C coupling step. The computational studies suggest that the electronics of both the aryl-benzamide and pyridine fragments of the aminoquinoline-benzamide ligand control the efficiency of the reaction.

Back to tab navigation

Supplementary files

Article information


Submitted
10 Apr 2020
Accepted
16 May 2020
First published
19 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Accepted Manuscript
Article type
Edge Article

Mechanistic Details of the Cobalt-Mediated Dehydrogenative Dimerization of Aminoquinoline-Directed Benzamides

L. Xu, E. E. L.-N. Liu, J. Bacsa, C. E. MacBeth and D. G. Musaev, Chem. Sci., 2020, Accepted Manuscript , DOI: 10.1039/D0SC02066D

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements