Structural and electronic control of the bidentate 1‐(2‐pyridyl)benzotriazole ligand in copper chemistry with application to catalysis in the A3 coupling reaction

Sampani, Stavroula I, Zdorichenko, Victor, Devonport, Jack, Rossini, Gioia, Leech, Matthew C, Lam, Kevin, Cox, Brian, Abdul-Sada, Alaa, Vargas, Alfredo and Kostakis, George E (2021) Structural and electronic control of the bidentate 1‐(2‐pyridyl)benzotriazole ligand in copper chemistry with application to catalysis in the A3 coupling reaction. Chemistry: A European Journal, 27 (13). pp. 4394-4400. ISSN 0947-6539

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Abstract

The hybrid bidentate 1‐(2‐pyridyl)benzotriazole (pyb) ligand was introduced into 3d transition metal catalysis. Specifically, [CuII(OTf)2(pyb)2]⋅2 CH3CN (1) enables the synthesis of a wide range of propargylamines by the A3 coupling reaction at room temperature in the absence of additives. Experimental and high‐level theoretical calculations suggest that the bridging N atom of the ligand imposes exclusive trans coordination at Cu and allows ligand rotation, while the N atom of the pyridine group modulates charge distribution and flux, and thus orchestrates structural and electronic precatalyst control permitting alkyne binding with simultaneous activation of the C−H bond via a transient CuI species.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
SWORD Depositor: Mx Elements Account
Depositing User: Mx Elements Account
Date Deposited: 10 Dec 2020 09:29
Last Modified: 09 Mar 2021 08:01
URI: http://sro.sussex.ac.uk/id/eprint/95628

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