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Computational Study of the Ni-Catalyzed C–H Oxidative Cycloaddition of Aromatic Amides with Alkynes

Omer, Humair M. and Liu, Peng (2019) Computational Study of the Ni-Catalyzed C–H Oxidative Cycloaddition of Aromatic Amides with Alkynes. ACS Omega, 4 (3). pp. 5209-5220. ISSN 2470-1343

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The mechanism of Ni-catalyzed ortho C(sp2)–H oxidative cycloaddition of aromatic amides with internal alkynes containing 2-pyridinylmethylamine directing group was investigated using density functional theory (DFT) calculations. The C–H cleavage step proceeds via σ-complex-assisted metathesis (σ-CAM) with an alkenyl-Ni(II) complex. This is in contrast to the more common carboxylate/carbonate-assisted concerted metalation–deprotonation mechanism in related Ni-catalyzed C–H bond functionalization reactions with N,N-bidentate directing groups. In this reaction, the alkyne not only serves as the coupling partner, but also facilitates the σ-CAM C–H metalation both kinetically and thermodynamically. The subsequent functionalization of the five-membered nickelacycle proceeds via alkyne insertion into the Ni–C bond to form a seven-membered nickelacycle. This process proceeds with high levels of regioselectivity to form a C–C bond with sterically more encumbered alkyne terminus. This unusual regioselectivity is due to steric repulsions with the directing group that is coplanar with the alkyne in the migratory insertion transition state. The C–N bond reductive elimination to form the isoquinolone cycloadduct is promoted by PPh3 complexation to the Ni center and the use of flexible 2-pyridinylmethylamine directing group. The origin of the cis–trans isomerism of alkene byproduct was also explained by computations.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Omer, Humair M.
Liu, Pengpengliu@pitt.edupengliu
Date: 2019
Date Type: Publication
Journal or Publication Title: ACS Omega
Volume: 4
Number: 3
Publisher: American Chemistry Society
Page Range: pp. 5209-5220
DOI or Unique Handle: 10.1021/acsomega.9b00030
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
Uncontrolled Keywords: chemistry
ISSN: 2470-1343
Official URL:
Funders: NSF
Article Type: Research Article
Date Deposited: 04 May 2020 17:12
Last Modified: 04 May 2020 17:12


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