Gold-Catalyzed Intermolecular Carboalkoxylation of Alkenes

Abstract

A gold-catalyzed intermolecular carboalkoxylation of ­alkenes has been developed. Readily available and inexpensive ­dimethyl acetals have been employed as a facile reagent to achieve the carboalkoxylation of alkenes.

Key words

gold catalysis - carboalkoxylation - alkenes - acetal - ­1,3-dimethoxyl compounds

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• 9 Gold-Catalyzed Intermolecular Carboalkoxylation of Alkenes; General Procedure: A mixture of [PicAuCl₂] (0.05 mmol, 5 mol%) and AgNTf₂ (0.10 mmol, 10 mol%) was stirred in toluene (2.0 mL) for 2 min, and then a solution of alkene (1.0 mmol) and acetal (1.5 mmol) in toluene (2.0 mL) was added. The system was heated to 50 °C until the starting material was completed consumed. The system was filtered through a short column of silica gel and eluted with diethyl ether. The concentrated crude product was purified by flash silica gel column chromatography using petroleum ether and diethyl ether as eluent.
• 10 Compound 3a (as a typical product): ¹H NMR (400 MHz, CDCl₃): δ (cis/anti) = 7.37–7.25 (m, 10 H), 4.06–4.03 (t, J = 7.2 Hz, 2 H), 3.14 (s, 6 H), 2.47–2.40 (m, J = 6.0 Hz, 1 H), 1.86–1.80 (m, J = 6.8 Hz, 1 H), 7.36–7.22 (m, 20 H); δ (anti) = 4.45–4.40 (m, J = 2.4 Hz, 2 H), 3.25 (s, 6 H), 2.00–1.97 (q, J = 2.4, 1.6 Hz, 2 H); ¹³C NMR (100 MHz, CDCl₃): δ (cis/anti) = 142.3, 141.6, 128.3, 127.6, 127.4, 126.8, 126.5, 80.8, 80.0, 56.7, 56.3, 47.6, 46.1; HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₇H₂₀NaO₂: 279.1356; found: 279.1344.

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