Palladium-Catalyzed [3+2] Cycloaddition of Vinylcyclopropane and Ketones

Abstract

A Pd-catalyzed [3+2] cycloaddition reaction of vinylcyclopropane and trifluoromethyl ketones as well as α-keto esters were developed, affording tetrahydrofurans in high yield.

Key words

palladium - [3+2] cycloaddition - vinylcyclopropane - trifluoromethyl ketone - α-keto ester - tetrahydrofuran

• References and Notes

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• 10 General Experimental Procedures for Products 3 To a flame-dried sealing tube were added Pd(OAc)₂ (2.25 mg, 0.01 mmol), (rac)-BINAP (12.45 mg, 0.02 mmol), and freshly distilled anhydrous tetrahydrofuran (1.0 mL). The resulting mixture was allowed to stir for 30 min. The ketone 2 (0.2 mmol) and vinylcyclopropane 1 (0.5 mmol) were added subsequently. The resulting reaction mixture was stirred at room temperature for 72 h. After the volatile was removed in vacuo, the ratio of two diastereoisomers was determined by crude ¹H NMR analysis. The yield was determined by NMR spectroscopy using mesitylene as the internal standard. Then the resulting residue was purified by preparative TLC to afford pure sample for characterization. 2-Phenyl-2-(trifluoromethyl)-5-vinyldihydrofuran-3,3(2H)-dicarbonitrile (3a) White solid, mp 48.5–48.7 °C, yield 89%, dr 1.3:1. ¹H NMR (400 MHz in CDCl₃; taken as a mixture of diastereomers): δ (minor diastereomer) = 7.70–7.75 (m, 2 H), 7.48–7.52 (m, 3 H), 5.96 (ddd, J = 17.2, 10.0, 6.8 Hz, 1 H), 5,51 (d, J = 18.4 Hz, 1 H), 5.38 (d, J = 10.4 Hz, 1 H), 5.07–4.99 (m, 1 H), 3.09–3.01 (m, 1 H), 2.88 (dd, J = 13.6, 8.4 Hz, 1 H); δ (major diastereomer) = 6.03 (ddd, J = 17.2, 10.0, 6.8 Hz, 1 H), 5.55 (d, J = 18.4 Hz, 1 H), 5.45 (d, J = 10.4 Hz, 1 H), 5.21–5.12 (m, 1 H), 3.31 (dd, J = 13.6, 8.4 Hz, 1 H), 2.87–2.79 (m, 1 H). ¹³C NMR (101 MHz in CDCl₃; taken as a mixture of diastereomers): δ = 134.8, 133.0, 132.4, 132.0, 130.7 (2 C), 129.0, 128.9, 126.5, 126.4, 124.8 (q, J = 291 Hz), 124.1 (q, J = 291 Hz), 120.9, 119.9, 112.7, 112.2, 111.7, 111.1, 90.3 (q, J = 29 Hz, 2 C), 81.7, 44.3 (2 C), 43.8, 42.2.¹⁹F NMR (376 MHz in CDCl₃; taken as a mixture of diastereomers): δ = –72.32, –74.07. IR (film): 1450, 1348, 1267, 1192, 1156, 1117, 1104, 1066, 1032, 1015, 999, 983, 942, 763, 725, 697 cm^–1. GC–MS (EI): m/z (rel.): 292 [M⁺], 223, 175 (100), 118, 105, 91, 77. HRMS (EI): m/z calcd for C₁₅H₁₁F₃N₂O [M⁺]: 292.0823; found: 292.0832.