Structural and Electronic Control of the Bidentate 1-(2-pyridyl)benzotriazole Ligand in Copper Chemistry with Application to Catalysis in the A3 Coupling Reaction

Stavroula I. Sampani, Victor Zdorichenko, Jack Devonport, Gioia Rossini, Matthew C. Leech, Kevin Lam, Brian Cox, Alaa Abdul-Sada, Alfredo Vargas, George E. Kostakis

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Pages (from-to)4394-4400
Number of pages7
JournalChemistry - A European Journal
Volume27
Issue number13
DOIs
Publication statusPublished - Mar 1 2021

Keywords

  • A coupling
  • N ligands
  • copper
  • density functional calculations
  • ligand effects

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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