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Synlett
DOI: 10.1055/a-2294-1643
DOI: 10.1055/a-2294-1643
letter
Microwave-Assisted Transfer Hydrogenation of Carbonyl and Nitro Compounds Using Bimetallic Ru(II) Cymene Complexes
This work was supported by the Science and Engineering Research Board (SERB), New Delhi through a J. C. Bose Fellowship grant to R.M. (SB/S2/JCB-85/2014). G.D. thanks the Council of Scientific and Industrial Research/University Grants Commission (CSIR/UGC), New Delhi and the Indian Institute of Technology Bombay (IIT Bombay) for a research fellowship.
Dedicated to Professor P. Selvam on the occasion of 65th Birthday.
Abstract
We report an investigation of the microwave-assisted catalytic transfer hydrogenation (TH) of carbonyl and nitro compounds by employing Ru(II) complexes: bimetallic [(p-cymene)2(RuCl)2L1]2X (X = BF4 (Cat2); X = PF6 (Cat3)) and mononuclear [(p-cymene)(RuCl)L2]BF4 (Cat4) (where L1 = N,N′-(3,3′,5,5′-tetraisopropyl-[1,1′-biphenyl]-4,4′-diyl)bis(1-(pyridin-2-yl)methanimine) and L2 = N-(2,6-diisopropylphenyl)-1-(pyridin-2-yl)methanimine). At a low catalyst loading of 0.01 mol% (Cat2/Cat3), a broad range of substrates, comprising aromatic as well as aliphatic ketones and aldehydes, undergo the TH reaction in a short reaction time of just 10 minutes. Additionally, chemoselective hydrogenation of nitroaromatic compounds is achieved under microwave irradiation in the presence of Cat2 within 5 minutes. Control experiments demonstrate that microwave heating conditions outperform conventional heating in terms of improved catalytic activity and reaction efficiency. The bimetallic catalyst Cat2 is used at a very low loading of 0.001 mol% to achieve high TONs and TOFs of 7.7 × 104 and 2.3 × 105 h–1, respectively, for the TH reaction. Spectrometry experiments involving trapping of intermediates are used to propose a mechanism for the TH of the carbonyl compounds.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2294-1643.
- Supporting Information
Publication History
Received: 27 January 2024
Accepted after revision: 25 March 2024
Accepted Manuscript online:
25 March 2024
Article published online:
19 April 2024
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