Issue 18, 2023

Cyclometalated C^N diphosphine ruthenium catalysts for Oppenauer-type oxidation/transfer hydrogenation reactions and cytotoxic activity

Abstract

The cyclometalated acetate ruthenium complexes [Ru(C^N)(η2-OAc)(dppb)] (dppb = 1,4-bis(diphenylphosphino)butane; HC^N = 2-phenylpyridine 1, benzo[h]quinoline 2, 1-phenylpyrazole 3, 2-phenyl-2-oxazoline 4) are easily obtained in 58–74% yield through a one-pot synthesis from [Ru(η2-OAc)2(dppb)] and the corresponding phenyl substituted N-heterocycle in methanol via elimination of HOAc. These complexes have been characterized by single crystal X-ray diffraction studies. Protonation of 2 with HCO2H (5 equiv.) in toluene affords the formate [Ru(C^N)(η2-HCO2)(dppb)] (5) isolated in 75% yield, without release of the HC^N ligand. The derivatives 1–4 display catalytic activity in the Oppenauer-type oxidation of secondary alcohols to ketones at S/C = 1000, using acetone or cyclohexanone as hydrogen acceptor and KOtBu as base in toluene, with TOF up to 12 000 h−1 for 4. Complexes 1–4 at S/C = 1000 are also active in the TH of carbonyl compounds to alcohols in 2-propanol employing NaOiPr, with TOF up to 14 300 h−1 for 4. The evaluation of the cytotoxic activity of these complexes against U87 glioblastoma cancer cell line via MTT test affords IC50 values ranging from 1.4 to 4.1 μM.

Graphical abstract: Cyclometalated C^N diphosphine ruthenium catalysts for Oppenauer-type oxidation/transfer hydrogenation reactions and cytotoxic activity

Supplementary files

Article information

Article type
Paper
Submitted
16 May 2023
Accepted
16 Aug 2023
First published
16 Aug 2023
This article is Open Access
Creative Commons BY-NC license

Catal. Sci. Technol., 2023,13, 5267-5279

Cyclometalated C^N diphosphine ruthenium catalysts for Oppenauer-type oxidation/transfer hydrogenation reactions and cytotoxic activity

D. Alessi, P. Del Mestre, E. Aneggi, M. Ballico, A. P. Beltrami, M. Busato, D. Cesselli, A. A. Heidecker, D. Zuccaccia and W. Baratta, Catal. Sci. Technol., 2023, 13, 5267 DOI: 10.1039/D3CY00676J

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