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Synlett 2023; 34(12): 1399-1402
DOI: 10.1055/s-0042-1752986
DOI: 10.1055/s-0042-1752986
cluster
Special Issue Honoring Masahiro Murakami’s Contributions to Science
1,4-Reduction of α,β-Unsaturated Ketones through Rhodium(III)-Catalyzed Transfer Hydrogenation
Financial support from the National Science Foundation of China (No. 21372188) and Hunan Normal University are greatly appreciated.
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Dedicated to Professor Masahiro Murakami on the occasion of his retirement from Kyoto University
Abstract
A rhodium(III)-catalyzed transfer hydrogenation of unsaturated ketones was developed. The simple catalytic system could be used for the 1,4-reduction of unsaturated cyclic, acyclic ketones, diketones, as well as β-ketoester, and a variety of functional groups were well-tolerated, affording products in moderate to excellent yields.
Key words
1,4-reduction - unsaturated ketone - rhodium(III) catalysis - transfer hydrogenation - isopropanolSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0042-1752986.
- Supporting Information
Publication History
Received: 19 July 2022
Accepted after revision: 29 August 2022
Article published online:
30 September 2022
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- 13 Typical Procedure To an oven-dried vial, 1-phenyl-3-(4-vinylphenyl)prop-2-en-1-one (1g′, 0.2 mmol, 46.9 mg), [(Cp*RhCl2)2] (0.006 mmol, 3.7 mg), and isopropanol (1.0 mL) were added. The vial was charged with N2 and sealed immediately. The mixture was stirred at 100 °C for 12 h. After the completion of the reaction, the mixture was cooled down to room temperature, filtered through a Celite pad, and washed with ethyl acetate. The filtrate was concentrated in vacuo, and the residue was purified by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate) to afforded 24.1 mg (51%) of 2g′ as an oil. 1H NMR (CDCl3, 400 MHz): δ = 7.97 (d, J = 5.6 Hz, 2 H), 7.56 (t, J = 5.8 Hz, 1 H), 7.48–7.44 (m, 2 H), 7.36 (d, J = 6.6 Hz, 2 H), 7.22 (d, J = 6.6 Hz, 2 H), 6.70 (dd, J = 14, 8.8 Hz, 1 H), 5.72 (d, J = 14 Hz, 1 H), 5.21 (d, J = 8.8 Hz, 1 H), 3.30 (t, J = 12.2 Hz, 2 H), 3.07 (t, J = 12.2 Hz, 2 H). 13C NMR (CDCl3, 126 MHz): δ = 199.2, 140.9, 136.8, 136.5, 135.5, 133.1, 128.6, 128.0, 126.3, 113.2, 40.3, 29.8 ppm. IR (KBr): νmax = 1680, 1630, 1600, 1579, 1508, 1448, 1206, 974, 742, 688 cm–1. HRMS (ESI): m/z calcd for C17H16O+ [M + H]+: 237.1274; found: 237.1271.
For reviews, see:
For a recent example, see:
For examples on selective transfer hydrogenation of α,β-unsaturated ketones using isopropanol as hydrogen source, see:
For reviews on ruthenium-catalyzed transfer hydrogenation, see: