Synthesis of 2,5-Disubstituted Dihydrofuran-3(2H)-ones via [2,3]-Sigmatropic Rearrangement of Oxonium Ylides Generated from α-Oxo Gold Carbenes

Abstract

Novel [2,3]-sigmatropic rearrangements of oxonium ylides generated from α-oxo gold carbenes were discovered. An ­efficient synthetic method of 2,5-disubstituted dihydrofuran-3(2H)-ones via gold-catalyzed intermolecular oxidation of the allyl homopropargyl ethers with N-oxide was developed. And the synthetic utility of the current method has been proved by concise formal synthesis of (±)-kumausallene.

Key words

carbenes - catalysis - dihydrofuran-3(2H)-ones - α-oxo gold carbenes - rearrangement

• References and Notes


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• 14 Procedure for the Gold-Catalyzed Rearrangement To the allyl homopropargyl ether 1b (15 mg, 0.065 mmol) in DCE (1.3 mL) were added 4c (25 mg, 0.13 mmol) and 3a (4 mg, 8 mol%), and the reaction mixture was heated at 60 °C for 15 h. The reaction mixture was quenched with 1 M HCl solution (5 mL) and extracted with EtOAc (3 × 5 mL). The combined organic layers were washed with brine (5 mL), dried over anhydrous MgSO₄, and condensed. The crude product was purified by flash column chromatography on silica gel (hexane–EtOAc, 20:1) to give trans-2b (6 mg) and cis-2b (4 mg) as yellow oils in 62% (trans/cis = 61:39).
• 15 Spectral Data Compound trans-2b (major): R_f  = 0.48 (hexane–EtOAc, 3:1). ¹H NMR (400 MHz, CDCl₃): δ = 7.36–7.26 (m, 5 H), 5.82 (dddd, J = 17.1, 10.1, 7.0, 7.0 Hz, 1 H), 5.14 (m, 2 H), 4.55 (m, 3 H), 4.14 (dd, J = 7.2, 4.8 Hz, 1 H), 3.72 (dd, J = 10.2, 3.4 Hz, 1 H), 3.54 (dd, J = 10.2, 3.8 Hz, 1 H), 2.57 (m, 3 H), 2.31 (m, 1 H). ¹³C NMR (100.6 MHz, CDCl₃): δ = 215.4, 137.9, 133.2, 128.6, 127.9, 127.6, 118.4, 79.6, 74.6, 73.6, 72.9, 38.8, 36.1. HRMS: m/z calcd for C₁₅H₁₈O₃Na [M + Na]⁺: 269.1148; found: 269.1147. Compound cis-2b (minor): R_f  = 0.44 (hexane–EtOAc, 3:1). ¹H NMR (400 MHz, CDCl₃): δ = 7.39–7.27 (m, 5 H), 5.82 (dddd, J = 17.2, 10.3, 6.9, 7.0 Hz, 1 H), 5.12 (m, 2 H), 4.62 (s, 2 H), 4.38 (m, 1 H), 3.91 (dd, J = 6.8, 4.4 Hz, 1 H), 3.67 (m, 2 H), 2.55 (m, 1 H), 2.49 (d, J = 6.0 Hz, 1 H), 2.37 (m, 2 H). ¹³C NMR (100.6 MHz, CDCl₃): δ = 214.9, 138.0, 133.2, 128.6, 127.9, 127.8, 118.2, 81.0, 75.2, 73.7, 71.6, 39.7, 35.5. IR (film): 3071, 3030, 2919, 2862, 1756, 1642, 1454, 1101, 920, 739, 698 cm^–1. HRMS: m/z calcd for C₁₅H₁₈O₃Na [M + Na]⁺: 269.1148; found: 269.1147.