Structural and Electronic Control of the Bidentate 1‐(2‐pyridyl)benzotriazole Ligand in Copper Chemistry with Application to Catalysis in the A3 Coupling Reaction. Issue 13 (26th January 2021)

• Record Type: Journal Article
• Authors: Sampani, Stavroula I.; Zdorichenko, Victor; Devonport, Jack; Rossini, Gioia; Leech, Matthew C.; Lam, Kevin; Cox, Brian; Abdul‐Sada, Alaa; Vargas, Alfredo; Kostakis, George E.
• Is Part Of: Chemistry. Volume 27:Issue 13(2021)
• Page Start: 4394
• Page End: 4400
• Publication Date: 2021-01-26
• Subjects: A3 coupling -- copper -- density functional calculations -- ligand effects -- N ligands; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202004781
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The hybrid bidentate 1‐(2‐pyridyl)benzotriazole (pyb) ligand was introduced into 3d transition metal catalysis. Specifically, [Cu II (OTf)2 (pyb)2 ]⋅ 2 CH3 CN (1 ) enables the synthesis of a wide range of propargylamines by the A 3 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 Cu I species. Abstract : Precatalyst control : [Cu II (OTf)2 (pyb)2 ]2 CH3 CN (1 ), in which pyb is 1‐(2‐pyridyl)benzotriazole, enables the synthesis of a wide range of propargylamines by the A 3 coupling reaction at room temperature in the absence of additives. The hybrid N, N′‐bidentate pyb ligand imposes exclusive trans coordination at Cu, can rotate and modulate charge distribution and flux, thus orchestrating structural and electronic precatalyst control permitting activation of the C−H bond.