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Synlett 2018; 29(06): 820-824
DOI: 10.1055/s-0036-1591521
DOI: 10.1055/s-0036-1591521
letter
Dual Iminium- and Lewis Base Catalyzed Morita–Baylis–Hillman Reaction on Cyclopent-2-enone
Financial support from the University of Florence and MIUR (PRIN2015, cod. 20157WW5EH) is acknowledged.
Further Information
Publication History
Received: 02 November 2017
Accepted after revision: 16 November 2017
Publication Date:
13 December 2017 (online)
Abstract
The application of iminium catalysis to the challenging Morita–Baylis–Hillman reaction on cyclopenten-2-one leads to the corresponding allylic alcohols in excellent yields. Experimental evidence shows that secondary amines act as co-catalysts activating the enone moiety towards the nucleophilic attack at the β-position by DABCO as the Lewis base catalyst, resulting in an augmented nucleophilic character towards the reaction with aldehydes.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591521.
- Supporting Information
-
References and Notes
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- 23 General Procedure for the Morita–Baylis–Hillman Reaction In a flask containing a solution of DABCO (0.12 mmol, 14 mg) in THF (0.5 mL) and 1 M aqueous solution of NaHCO3 (2 mL), pyrrolidine (0.12 mmol, 10 μL), cyclopent-2-enone (0.6 mmol), and the aldehyde (1.8 mmol) were successively added. The reaction was stirred at room temperature for 40 h. Then, ethyl acetate (20 mL) was added, and the organic phase was washed with 1 M HCl, sat. aqueous NaHCO3, and brine. The organic phase was dried over Na2SO4, filtered, concentrated under reduced pressure, and the crude product was purified by flash chromatography column (FCC). 2-[Hydroxy(3,4-dimethoxyphenyl)methyl]cyclopent-2-enone (13) Obtained in 37% yield. 1H NMR (400 MHz, CDCl3): δ = 6.95–6.81 (m, 4 H), 5.50 (s, 1 H), 3.87 (s, 3 H), 3.86 (s, 3 H) 2.58 (m, 2 H), 2.45 (m, 2 H). 13C NMR (50 MHz, CDCl3): δ = 209.7, 159.3, 149.1, 148.6, 147.8, 133.9, 118.6, 110.9, 109.5, 69.7, 55.9 (2 C), 35.3, 26.6. ESI-MS: m/z (%) = 271.17 (100) [M + Na]+. Anal. Calcd for C14H16O4 (248.27): C, 67.73; H, 6.50. Found: C, 67.80; H, 6.58. 2-[Hydroxy(2-thienyl)methyl]cyclopent-2-enone (15) Obtained in 69% yield. 1H NMR (400 MHz, CDCl3): δ = 7.45 (m, 1 H), 7.27–7.23 (m, 1 H), 7.00–6.95 (m, 2 H), 5.81 (s, 1 H), 3.68 (br, 1 H), 2.65–2.62 (m, 2 H), 2.49–2.47 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 209.3, 159.6, 146.9, 145.1, 126.7, 125.2 124.7, 66.2, 35.3, 26.7. ESI-MS: m/z (%) = 217.08 (100) [M + Na]+. Anal. Calcd for C10H10O2S (442.52): C, 61.83; H, 5.19. Found: C, 62.00; H, 5.28.
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