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Synlett 2025; 36(10): 1391-1396
DOI: 10.1055/s-0043-1773533
DOI: 10.1055/s-0043-1773533
letter
Copper-Catalyzed Decarboxylative Phosphorylation of Coumarin-3-carboxylic Acids
R.N.G. is grateful to KCG, SHODH (Scheme of Developing High-Quality Research), Gujarat, India, for financial assistance.
Abstract
We report a novel, efficient, one-pot, copper-catalyzed, decarboxylative strategy for the cross-coupling of coumarin 3-carboxylic acids with H-phosphonates. The approach involves a decarboxylation followed by phosphonation through a radical pathway, and uses an inexpensive copper catalyst. Optimizations were carried out using various copper catalysts, oxidants, and solvents. The reaction is highly effective, with a broad functional-group tolerance, and affords good to excellent yields. This transformation provides a versatile and useful synthetic pathway for the construction of bioactive scaffolds with valuable C–P bonds.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1773533
- Supporting Information
Publikationsverlauf
Eingereicht: 11. Februar 2025
Angenommen nach Revision: 03. März 2025
Artikel online veröffentlicht:
02. April 2025
© 2025. Thieme. All rights reserved
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- 52 Compounds 3a–l; General Procedure The appropriate H-phosphinate 2 (0.30 mmol), CuCl (15 mol%), and DTBP (4.0 equiv) were added to a solution of the appropriate coumarin-3-carboxylic acid 1 53 (0.25 mmol) in MeCN (2 ml) in a glass reaction tube, and the resulting mixture was stirred at r.t. for 30 min under air. The mixture was then heated at 110 °C in an oil bath for 18 h until the reaction was complete (TLC). The resulting mixture was cooled to r.t. and poured into ice-cold water (10–15 mL). The mixture was extracted by EtOAc and brine (3 × 15 mL), and the organic layer was separated, dried (Na2SO4), filtered, and concentrated under reduced pressure. Finally, the crude residue was purified by column chromatography. Diethyl (2-Oxo-2H-chromen-3-yl)phosphonate (3a) Off-white solid; yield: 72%; mp 74–75 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 8.56 (d, J P–H = 17.1 Hz, 1 H), 7.57–7.66 (m, 2 H), 7.29-7.35 (m, 2 H), 4.20-4.33 (m, 4 H, 2CH2), 1.40 (t, J H–H = 7.0 Hz, 6 H, 2CH3). 13C NMR (100 MHz, DMSO-d 6): δ = 157.89 (d, J P–C = 14.2 Hz), 155.71, 154.11 (d, J P–C = 6.7 Hz), 134.38, 129.65, 125.06, 119.21, 118.48 (d, J P–C = 14.1 Hz), 117.08 (d, J P–C = 19.9 Hz), 64.29 (d, J P–C= 6.1 Hz), 16.42 (d, J P–C = 6.2 Hz). HRMS (ESI): m/z [M + H]+ calcd for C13H16O5P: 283.0730; found: 283.0735.
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