Dehydrogenative Coupling for Synthesis of Quinazolin-4(3H)-ones via Tandem Reaction using Ruthenium(II)-Phenyl-Azo-Naphthaldoxime: An Experimental and Theoretical Investigation.

Autor: Halder S; Department of Chemistry, Jadavpur University, Kolkata, 700032, India., Naskar S; Department of Chemistry, Jadavpur University, Kolkata, 700032, India., Jana D; Department of Chemistry, Jadavpur University, Kolkata, 700032, India., Kanrar G; Department of Chemistry, St. Xavier's College (Autonomous), Kolkata, 700016, India., Mandal SC; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA., Roy S; Department of Chemistry, The ICFAI University Tripura, Agartala, Tripura, 799210, India., Bharadwaj N; Department of Chemistry, Indian Institute of Technology (IIT) Indore, Indore, Madhya Pradesh, 453552., Pramanik K; Department of Chemistry, Jadavpur University, Kolkata, 700032, India., Ganguly S; Department of Chemistry, St. Xavier's College (Autonomous), Kolkata, 700016, India.
Jazyk: angličtina
Zdroj: Chemistry, an Asian journal [Chem Asian J] 2024 Nov 28, pp. e202401278. Date of Electronic Publication: 2024 Nov 28.
DOI: 10.1002/asia.202401278
Abstrakt: The bidentate N, N, donor phenyl-azo-naphthaldoxime NpLH, 1 was used to synthesize the ruthenium(II) complex trans-[Ru(NpL)(CO)Cl(PPh 3 ) 2 ], 2. It has been characterized by SCXRD, electrochemical and spectral studies. Computational analysis indicates that the low-lying π*-LUMO of the complex has substantial azo-character of coordinated ligand. This property has been exploited to form an efficient electron transfer pre-catalyst to effectuate dehydrogenative functionalization of a large number of benzyl alcohols to quinazolin-4(3H)-ones via condensation with diverse o-amino benzamides as well as N-substituted benzamides under aerobic conditions (57 entries). A reaction mechanism has been projected via isolation of intermediates and certain control experiments. Furthermore, it has been substantiated by theoretical scrutiny using density functional theory (DFT) calculation. The catalytic cycle involves stepwise hydrogen atom transfer (HAT) from benzyl alcohols to the N azo atoms of the coordinated ligand with subsequent removal of the H-atoms from the N azo atoms to regenerate the active catalyst.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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