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DOI: 10.1055/s-0042-1752986
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Special Issue Honoring Masahiro Murakami’s Contributions to Science

1,4-Reduction of α,β-Unsaturated Ketones through Rhodium(III)-Catalyzed Transfer Hydrogenation

Xuewen Yu
a   Department of Environmental Monitoring, Changsha Environmental Protection College, Changsha 410004, P. R. of China
,
Saihong Wan
b   Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, Hunan Normal University, Changsha 410081, P. R. of China
c   College of Chemical Engineering, Xiangtan University, Xiangtan 411105, P. R. of China
,
Wang Zhou
b   Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, Hunan Normal University, Changsha 410081, P. R. of China
c   College of Chemical Engineering, Xiangtan University, Xiangtan 411105, P. R. of China
› Author Affiliations
Financial support from the National Science Foundation of China (No. 21372188) and Hunan Normal University are greatly appreciated.


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.

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.