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DOI: 10.1055/a-1539-9116
Copper-Catalyzed Cross-Dehydrogenative Coupling of α-Hydroxy Esters with Nitromethane
This work was supported by the Opening Project of Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education (LYJ1902).
Abstract
An efficient copper-catalyzed tandem oxidation/nitroaldol reaction of hydroxyl compounds with nucleophiles is developed. In this work, β-nitro-α-hydroxy esters were prepared via cross-dehydrogenative coupling reaction using α-hydroxy esters as hydroxy compounds and nitromethane as a nucleophile. The reaction is believed to undergo an oxidation of the hydroxy group and then an addition of the generated carbonyl group. It is an example of CDC reactions related to hydroxy compounds via carbonyl intermediates.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1539-9116.
- Supporting Information
Publication History
Received: 29 May 2021
Accepted after revision: 29 June 2021
Accepted Manuscript online:
29 June 2021
Article published online:
23 July 2021
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Methyl 2-Hydroxy-3-nitro-2-phenylpropanoate (2a): Typical Procedure
Methyl 2-hydroxy-2-phenylacetate (166.2 mg, 1.0 mmol, 1.0 equiv.), NaHCO3 (84.0 mg, 1.0 mmol, 1.0 equiv.), nitromethane (1.0 mL), aqueous tert-butyl hydroperoxide (70% solution in water, 321.9 mg, 2.5 mmol, 2.5 equiv.), and CuO (15.9 mg, 0.2 mmol, 0.2 equiv.) were added to a flask successively. Then the mixture was heated to 80 °C and stirred for 5 h. After that, the mixture was cooled to room temperature. Afterwards 10.0 mL of ethyl acetate and 10 mL of Na2S2O3 aqueous solution (0.5 mol/L) were added to the flask, and the organic layer was washed with brine, dried over anhydrous Na2SO4, filtered, concentrated, and purified by flash column chromatography with silica gel (200–300 mesh) using petroleum ether/ethyl acetate (8:1) to give a light yellow solid; yield 136.4 mg (61%), mp 85–86 °C.
1H NMR (600 MHz, CDCl3): δ = 7.75 (d, J = 8.4 Hz, 2 H), 7.30 (d, J = 8.4 Hz, 2 H), 7.28–7.23 (m, 3 H), 7.22–7.16 (m, 2 H), 4.93–4.80 (m, 1 H), 4.11 (d, J = 6.6 Hz, 2 H), 2.44 (s, 3 H). 13C NMR (150 MHz, CDCl3): δ = 143.6, 136.9, 136.4, 129.9, 128.8, 128.0, 127.3, 47.4, 21.7. HRMS (ESI): m/z [M – H]– calcd for C10H10NO5: 224.0559; found: 224.0558.