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Structural and Electronic Control of the Bidentate 1-(2-pyridyl)benzotriazole Ligand in Copper Chemistry with Application to Catalysis in the A3 Coupling Reaction |
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| Authors: | Stavroula I Sampani Dr Victor Zdorichenko Jack Devonport Gioia Rossini Dr Matthew C Leech Dr Kevin Lam Prof Brian Cox Dr Alaa Abdul-Sada Dr Alfredo Vargas Dr George E Kostakis |
| Institution: | 1. Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, BN1 9QJ UK;2. Photodiversity Ltd. c/o Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, BN1 9QJ UK;3. School of Science, Department of Pharmaceutical Chemical and Environmental Sciences, University of Greenwich, Central Avenue, Chatham Maritime, ME4 4TB UK |
| 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. |
| Keywords: | A3 coupling copper density functional calculations ligand effects N ligands |