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

Xuewen Yu; Saihong Wan; Wang Zhou

doi:10.1055/s-0042-1752986

Synlett, Inhaltsverzeichnis

Synlett 2023; 34(12): 1399-1402
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

Authors

Xuewen Yu∗

^aDepartment of Environmental Monitoring, Changsha Environmental Protection College, Changsha 410004, P. R. of China
Saihong Wan

^bKey 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

^cCollege of Chemical Engineering, Xiangtan University, Xiangtan 411105, P. R. of China
Wang Zhou ∗

^bKey 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

^cCollege of Chemical Engineering, Xiangtan University, Xiangtan 411105, P. R. of China

Abstract

Alle Artikel dieser Rubrik

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 - isopropanol

Volltext

Referenzen

References and Notes

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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): ν_max = 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.

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