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

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

Publikationsverlauf

Eingereicht: 19. Juli 2022

Angenommen nach Revision: 29. August 2022

Artikel online veröffentlicht:
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): 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.