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Synlett
DOI: 10.1055/a-2517-2139
DOI: 10.1055/a-2517-2139
letter
Emerging Trends in Organic Chemistry: A Focus on India
Baylis–Hillman Adducts as a Valuable Source for Synthesis of Functionalized [4,4,4]-Propellone Dilactone Derivatives
We thank to University Grants Commission (UGC), New Delhi for funding this project. M.P. and D.M. thank Central University Gujerat for their non-net fellowship.
Abstract
A simple and facile synthesis of functionalized [4,4,4]-propellone dilactone derivatives through dialkylation of cyclic 1,3-diketones with Baylis–Hillman adducts and subsequent dilactonization is described. This methodology is appealing because it is reliable and scalable (the products can be synthesized on a gram scale). The tricyclic products can be exploited for their biological activity.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2517-2139.
- Supporting Information
Publication History
Received: 09 December 2024
Accepted after revision: 15 January 2025
Accepted Manuscript online:
15 January 2025
Article published online:
28 February 2025
© 2025. Thieme. All rights reserved
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- 12 Di-tert-butyl (2E,2′E)-2,2′-[(2,6-Dioxocyclohexane-1,1-diyl)di(methylene)]bis(3-phenylacrylate) (3a); Typical Procedure Oil-free NaH (10 mmol, 0.24 g) was added to a stirred solution of cyclohexane-1,3-dione (2a; 2mmol, 0.234 g) in anhyd toluene, and the mixture was refluxed for 1 h under N2. tert-Butyl 3-acetoxy-2-methylene-3-phenylpropanoate (5 mmol, 1.38g) was then added and the mixture was stirred and refluxed for 30 h until the reaction was complete (TLC). The reaction was then quenched 1% aq AcOH (50 mL), and the organic layer was extracted with Et2O (3 × 25 mL). The combined organic layer was washed with H2O (20 mL), dried (Na2SO4), and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, 8% EtOAc–hexanes) to give a colorless solid; yield: 72%; mp 83–90 °C. IR (ATR): l max: 2976, 1693, 1722, 1156, 780 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.37 (s, 2 H), 7.20 (m, 6 H), 7.06–7.10 (m, 4 H), 2.77 (s, 4 H), 2.63 (t, J = 6.7 Hz, 4 H), 2.08 (m, 2 H), 1.39 (s, 18 H). 13C NMR (125 MHz, CDCl3): δ = 208.88, 167.81, 140.20, 135.78, 130.11, 129.11, 128.35, 127.87, 81.09, 66.23, 37.74, 31.35, 28.10, 17.62. HRMS (ESI): m/z [M + H]+ calcd C34H41O6: 545.2898; found: 545.2899. (4E,8E)-4,8-Dibenzylidene-2,10-dioxatricyclo[4.4.4.01,6]tetradecane-3,9,14-trione (4a); Typical Procedure TFA (5mmol, 0.57 g) was added to a stirred solution of 3a (1 mmol, 0.54 g) in DCE (5 mL) and the mixture was stirred at r.t. for 15 min. TFAA (2.5 mmol, 0.52 g) was then added and the mixture was refluxed for 3 h until the reaction was complete (TLC). The solvent was removed under reduced pressure and the residue was diluted with H2O (20 mL) and extracted with Et2O (3 × 25 mL). The combined organic layer was washed with sat. aq NaHCO3 (20 mL) and then dried (Na2SO4) and concentrated. The crude product was dissolved in Et2O (5 mL) precipitated by addition of pentane. The precipitate was collected by filtration and dried in a high vacuum to give an off-white solid; yield: 65%; mp 214–218 °C. IR (ATR): l max: 2934, 1728, 1274, 985, 833 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.97 (s, 2 H), 7.34–7.40 (m, 10 H), 3.38 (dd, J = 17.1, 2.2 Hz, 2 H), 2.66 (d, J = 2.3 Hz, 1 H), 2.58–2.64 (m, 3 H), 2.30 (dd, J = 7.2, 5.4 Hz, 2 H), 1.97–2.04 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 205.89, 163.36, 145.55, 134.13, 130.61, 130.25, 128.96, 119.54, 105.75, 49.71, 35.10, 32.74, 29.92, 18.43. HRMS (ESI): m/z [M + H]+ calcd for C26H23O5: 415.1540; found: 415.1535.