Nucleophilic Catalysis in the Enantioselective Synthesis of α-Methylidene-δ-lactones

Abstract

A new method for the preparation of optically active ­α-methyl­idene-δ-lactones is presented. The developed strategy utilizes an intramolecular Rauhut–Currier reaction for a facile construction of the α-methylidene-δ-lactone framework. The reaction is catalyzed by a chiral phosphine and employs the principles of nucleophilic catalysis. It benefits from operational simplicity and uses readily available starting materials.

Key words

asymmetric synthesis - nucleophilic catalysis - Rauhut–­Currier reaction - α-methylidene-δ-lactones - phosphine-mediated reactions

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• 15 During our work on the enantioselective synthesis of α-methylidene-δ-lactones via the intramolecular Rauhut–Currier reaction a similar contribution appeared in the literature: Scanes RJ. H, Grossmann O, Grossmann A, Spring DR. Org. Lett. 2015; 17: 2462
• 16 Representative Procedure An ordinary screw-cap vial was charged with a magnetic stirring bar, the corresponding acrylate 1 (0.15 mmol), the catalyst 3c (0.03 mmol), and CH₂Cl₂ (0.6 mL). The reaction mixture was stirred at –25 °C and monitored by ¹H NMR spectroscopy. When the signals of the starting acrylate 1 were no longer observed in the spectra of a crude reaction mixture it was directly subjected to flash chromatography on a silica gel to afford a target product 2. Following the general procedure, 2a was isolated by flash chromatography on silica (CH₂Cl₂–MeOH, 99:1) in 80% yield after 4 d as an amorphous white solid. ¹H NMR (700 MHz, CDCl₃): δ = 7.87–7.84 (m, 2 H), 7.57–7.53 (m, 1 H), 7.45–7.41 (m, 2 H), 7.30–7.28 (m, 1 H), 7.27–7.24 (m, 1 H), 7.12–7.07 (m, 2 H), 6.40 (s, 1 H), 5.92 (s, 1 H), 4.54 (t, J = 6.6 Hz, 1 H), 3.44 (dd, J = 17.4, 7.2 Hz, 1 H), 3.30 (dd, J = 17.4, 6.1 Hz, 1 H).¹³C NMR (176 MHz, CDCl₃): δ = 196.3, 163.2, 150.6, 136.5, 135.8, 133.5, 129.8, 128.7 (2C), 128.7, 128.1 (2 C), 128.0, 125.2, 124.9, 117.3, 46.0, 38.2. HRMS: m/z calcd for [C₁₈H₁₄O₃ + H]⁺: 279.1016; found: 279.1010. The er was determined by HPLC using a Chiralpak IA column (hexane–i-PrOH = 90:10); flow rate 1.0 mL/min; t _R (major) = 16.0 min, t _R (minor) = 14.4 min (89:11 er). [α]_D ²⁰ 76.2 (c 0.5, CHCl₃).
• 17 For 2b: [α]_D ²⁰ 76.2 (c 0.5, CHCl₃); lit.¹⁵ [α]_D ²⁰ 138.0 (c 0.1, CHCl₃).