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, Table of Contents

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

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

› Author Affiliations

Abstract

All articles of this category

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

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References

References and Notes

1a Patai S, Rappoport Z. In The Chemistry of Enones . John Wiley & Sons; Chichester: 1989
1b Nashimura S. In Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis. Wiley-Interscience; New York: 2001
1c de Vries JG, Elsevier CJ. In The Handbook of Homogeneous Hydrogenation . Wiley-VCH; Weinheim: 2007

2a Farrar-Tobar RA, Dell'Acqua A, Tin S, de Vries JG. Green Chem. 2020; 22: 3323
2b Talwar D, Wu X, Saidi O, Salguero NP, Xiao J. Chem. Eur. J. 2014; 20: 12835 ; and references therein

For reviews, see:

3a Shi Z, Li N, Lu H.-K, Chen X, Zheng H, Yuan Y, Ye K.-Y. Curr. Opin. Electrochem. 2021; 28: 100713
3b Hollmann F, Opperman DJ, Paul CE. Angew. Chem. Int. Ed. 2021; 60: 5644
3c Lipshutz BH. Copper(I)-Mediated 1,2- and 1,4-Reductions. In Modern Organocopper Chemistry. Krause N. Wiley-VCH; Weinheim: 2002: 167

For a recent example, see:

3d Gu Y, Norton JR, Salahi F, Lisnyak VG, Zhou Z, Snyder SA. J. Am. Chem. Soc. 2021; 143: 9657

4a Baráth E. Catalysts 2018; 8: 671
4b Wang D, Astruc D. Chem. Rev. 2015; 115: 6621

5a Aboo AH, Bennett EL, Deeprose M, Robertson CM, Iggo JA, Xiao J. Chem. Commun. 2018; 54: 11805
5b Wu X, Li X, Zanotti-Gerosa A, Pettman A, Liu J, Mills AJ, Xiao J. Chem. Eur. J. 2008; 14: 2209
5c Murata K, Ikariya T, Noyori R. J. Org. Chem. 1999; 64: 2186

6 Manna S, Antonchick AP. ChemSusChem 2019; 12: 3094

7a Garg N, Sarkar A, Sundararaju B. Coord. Chem. Rev. 2021; 433: 213728
7b Trincado M, Banerjeea D, Grützmacher H. Energy Environ. Sci. 2014; 7: 2464

8 Aboo AH, Begum R, Zhao L, Farooqi ZH, Xiao J. Chin. J. Catal. 2019; 40: 1795

For examples on selective transfer hydrogenation of α,β-unsaturated ketones using isopropanol as hydrogen source, see:

9a Lator A, Gaillard S, Poater A, Renaud J.-L. Chem. Eur. J. 2018; 24: 5770
9b Gliński M, Ulkowska U. App. Catal., A 2018; 554: 117
9c Chen S.-j, Lu G.-p, Cai C. RSC Adv. 2015; 5: 13208
9d Mertens PG. N, Poelman H, Ye X, Vankelecom IF. J, Jacobs PA, De Vos DE. Catal. Today 2007; 122: 352
9e Braun F, Di Cosimo JI. Catal. Today 2006; 116: 206
9f Di Cosimo JI, Acosta A, Apesteguía CR. J. Mol. Catal. A: Chem. 2005; 234: 111
9g Mizushima E, Yamaguchi M, Yamagishi T. J. Mol. Catal. A: Chem. 1999; 148: 69
9h Bianchini C, Glendenning L, Zanobini F, Farnetti E, Graziani M, Nagy E. J. Mol. Catal. A: Chem. 1998; 132: 13

10 Crabtree RH. Chem. Rev. 2017; 117: 9228

For reviews on ruthenium-catalyzed transfer hydrogenation, see:

11a Ritleng V, de Vries JG. Molecules 2021; 26: 4076
11b Conley BL, Pennington-Boggio MK, Boz E, Williams TJ. Chem. Rev. 2010; 110: 2294

12 Carbonyl reduction of 1a and the subsequent condensation with isopropanol may deliver allylic isopropyl ether (Scheme 2). See: Sai M. Adv. Synth. Catal. 2018; 360: 3482
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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