Ni(OTf)₂-Catalyzed Michael Addition Reactions of 4-Hydroxycoumarins to α,β-Unsaturated 2-Acyl Imidazoles

Abstract

An efficient Michael addition of 4-hydroxycoumarins to α,β-unsaturated 2-acyl imidazoles catalyzed by Ni(OTf)₂ as a Lewis acid has been developed. A series of 4-hydroxycoumarin derivatives were obtained in excellent yields (up to 96%) with a 2 mol% catalyst loading under mild conditions. Additionally, when a chiral-at-metal rhodium complex was used as the catalyst, moderate enantioselectivity was observed (74% ee).

Key words

hydroxycoumarins - imidazoles - Michael addition - Lewis acid - rhodium catalysis - nickel catalysis

Publication History

Received: 24 March 2024

Accepted after revision: 20 April 2024

Accepted Manuscript online:
20 April 2024

Article published online:
14 June 2024

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• 11 4-Hydroxy-3-[3-(1-methyl-1H-imidazol-2-yl)-3-oxo-1-phenylpropyl]-2H-chromen-2-one (3a); Typical Procedure A dried 25 mL Schlenk tube was charged with 2-acyl imidazole 1a (0.20 mmol), 4-hydroxycoumarin (2a; 0.22 mmol), and Ni(OTf)₂ (1.4 mg, 2 mol%). The tube was then purged with argon and DCE (0.8 mL) was added. The resulting mixture was stirred at 30 °C for 12 h under argon until the reaction was complete (TLC), then cooled to r.t. The resulting mixture was purified by flash column chromatography [silica gel, CH₂Cl₂–MeOH (100:1 to 20:1)]; to afford a white solid; yield: 71.6 mg (95%); mp 184.0–185.7 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.01 (dd, J = 8.0, 1.6 Hz, 1 H), 7.61–7.56 (m, 1 H), 7.46 (s, 1 H), 7.38 (d, J = 7.6 Hz, 2 H), 7.34 (t, J = 8.0 Hz, 2 H), 7.24 (t, J = 8.0 Hz, 2 H), 7.15 (d, J = 7.6 Hz, 1 H), 7.11 (s, 1 H), 5.09 (t, J = 7.2 Hz, 1 H), 4.20 (dd, J = 17.2, 6.8 Hz, 1 H), 3.89 (d, J = 8.0 Hz, 1 H), 3.84 (s, 3 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 191.23, 162.20, 160.91, 152.54, 143.28, 142.95, 132.27, 128.99, 128.43, 127.98, 126.38, 124.22, 123.81, 116.68, 116.60, 108.53, 40.99, 35.99, 35.61. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₂H₁₉N₂O₄: 375.1339; found: 375.1342.