Thulium Triflate Catalyzed Hydration of 2-Substituted 4-Alkynones

Abstract

We report on a facile synthetic route for the preparation of substituted 1,4-diketones by thulium triflate mediated hydration of substituted 4-alkynones in MeNO₂ at 25 °C for five hours. The products were obtained in moderate to high yields.

Key words

diketones - thulium triflate - hydration - alkynone - pyridazine

• References and Notes


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• 25 Representative Synthetic Procedure of Skeleton 4 Tm(OTf)₃ (62 mg, 0.1 mmol) was added to a solution of 3 (1.0 mmol) in MeNO₂ (5 mL) at r.t. The reaction mixture was stirred at reflux for 3 h. The reaction mixture was cooled to r.t. The solvent of reaction mixture was concentrated and extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford the crude product under reduced pressure. Purification on silica gel (hexanes–EtOAc = 8:1 to 3:1) afforded 4. Compound 4a: R_f = 0.3 (hexanes–EtOAc = 8:1); yield 88% (290 mg); colorless oil. ESI-HRMS: m/z calcd for C₁₈H₁₉O₄S [M⁺ + 1]: 331.1004; found: 331.1010. ¹H NMR (400 MHz, CDCl₃): δ = 7.91 (d, J= 8.8 Hz, 2 H), 7.58–7.54 (m, 3 H), 7.43–7.39 (m, 2 H), 7.24 (d, J = 8.4 Hz, 2 H), 5.51 (dd, J = 2.8, 10.8 Hz, 1 H), 3.49 (dd, J = 10.8, 18.0 Hz, 1 H), 3.29 (dd, J = 2.8, 18.0 Hz, 1 H), 2.40 (s, 3 H), 2.16 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 203.79, 191.59, 145.60, 136.58, 133.68, 133.54, 129.68 (2×), 129.36 (2×), 129.17 (2×), 128.49 (2×), 65.55, 41.87, 29.55, 21.64. Compound 4b: R_f = 0.3 (hexanes–EtOAc = 8:1); yield 86% (299 mg); colorless oil. ESI-HRMS: m/z calcd for C₁₈H₁₈FO₄S [M⁺ + 1]: 349.0910; found: 349.0918. ¹H NMR (400 MHz, CDCl₃): δ = 7.99–7.94 (m, 2 H), 7.57 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 8.8 Hz, 2 H), 7.13–7.07 (m, 2 H), 5.43 (dd, J = 2.8, 10.8 Hz, 1 H), 3.47 (dd, J = 10.8, 18.0 Hz, 1 H), 3.27 (dd, J = 2.8, 18.0 Hz, 1 H), 2.42 (s, 3 H), 2.15 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 203.81, 190.02, 166.13 (d, J = 255.5 Hz), 145.77, 133.36, 133.03 (d, J = 3.0 Hz), 132.97 (d, J = 9.1 Hz, 2×), 130.53, 129.74, 129.35, 128.84, 115.71 (d, J = 21.9 Hz, 2×), 65.58, 41.99, 29.49, 21.65.

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