Europium-Catalyzed Intramolecular Addition of Carboxylic Acid to Nonactivated Alkenes: An Efficient Route to Aryl-Substituted γ-Butyrolactone

Abstract

Europium(III)triflate has been proved to be an effective catalyst for intramolecular cyclization of aryl-substituted carboxylic acid to afford arylated γ-butyrolactone. Various attractive features, such as broad substrate scope, a wide range of functional group tolerance, operational simplicity, complete atom economy, and good-to-excellent yields have made this new protocol more appealing. Moreover, this method provides a practical alternative to the existing catalysts.

Key words

γ-butyrolactones - lanthanide catalyst [Eu(OTf)₃] - ω-alkenoic acid - intramolecular hydroacyloxylation reaction - O-containing heterocycles

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• 13 Typical Procedure for the Preparation of Reference Compound 5-Methyl-4-phenyldihydrofuran-2(3H)-one (2a) A chlorobenzene (0.2 M) solution of the 3-phenylpent-4-enoic acid (1a, 50 mg, 0.284 mmol) was taken in a 10 mL sealed tube, and Eu(OTf)₃ (5 mol%) was added to it. Nitrogen gas was flushed into it; the tube was closed and placed it in a silicon oil bath. After 7 h heating the starting material was completely consumed as indicated by TLC, and the reaction was quenched by adding water. Compound was extracted with ethyl acetate (3 × 20 mL). Combined organic layer was washed with brine solution, dried over sodium sulfate, and evaporated to dryness. The crude product was purified on silica gel (mesh 100–200) column chromatography using ethyl acetate in petroleum ether (1:2) as eluent to afford 2a (35 mg, 70%) as yellow oil. IR: 1775 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.39–7.24 (m, 5 H), 4.55 (ddd, J = 12, 8.6, 6.2 Hz, 1 H), 3.25 (td, J = 11.2, 6.2 Hz, 1 H), 2.95 (dd, J = 16, 8.4 Hz, 1 H), 2.79 (dd, J = 16, 11.2 Hz, 1 H), 1.42 (d, J = 6.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 175.5, 138.2, 129.1, 127.8, 83.2, 49.7, 37.5, 19.2. HRMS: m/z [M + H]⁺ – H₂O calcd for C₁₁H₁₂O₂: 159.0837; found: 159.0843.