Palladium(0)-Catalyzed Diastereoselective (3+2) Cycloadditions of Vinylcyclopropanes with Sulfonyl-Activated Imines

Abstract

We report herein a palladium(0)-catalyzed (3+2)-cycloaddition process between vinylcyclopropanes and cyclic or acyclic sulfonylimines. This reaction, which operates under low catalyst loading and practical reaction conditions, gives access to a wide variety of N-heterocyclic derivatives in good to excellent yields and high levels of diastereoselectivity.

Key words

palladium(0)-catalysis - (3+2) cycloaddition - vinylcyclopropanes - sulfonylimines - N-heterocycles

• References and Notes


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• 22 General Procedure for the Palladium-Catalyzed (3+2) Cyclo­addition of VCPs with Sulfonyl-Activated Imines In a screw-capped vial, vinylcyclopropane (0.44 mmol, 1.1 equiv), the desired sulfonylimine (0.40 mmol, 1.0 equiv), and toluene (800 μL) were successively added. The resulting mixture was stirred at room temperature for 5 min, before a solution of Pd₂(dba)₃·CHCl₃ (4.1 mg, 0.004 mmol, 0.01 equiv) and dppe (3.2 mg, 0.008 mmol, 0.02 equiv) in toluene (800 μL), previously stirred at room temperature for 25 min, was transferred via cannula. The cannula was washed with additional toluene (400 μL) (total volume of toluene = 2.0 mL), and the mixture was stirred at room temperature (for the appropriate reaction time see Supporting Information). CH₂Cl₂ (10 mL) was then added, and the mixture was loaded onto a small silica plug, eluted with additional CH₂Cl₂ (40 mL), and concentrated under reduced pressure. After measurement of the diastereomeric ratio by ¹H NMR spectroscopy, the resulting crude mixture was purified by either flash column chromatography or trituration in hexane to afford the desired cycloadduct. Cycloadduct 3aa Following the typical procedure, compound 3aa was obtained as a white solid (119 mg, 36:1 dr, 99% yield) after flash column chromatography (toluene/cyclohexane/ethyl acetate = 19:19:2 to 9:9:2). Analytical Data ¹H NMR (400 MHz, CDCl₃): δ = 7.58–7.47 (m, 2 H), 7.41 (td, J = 7.7, 1.0 Hz, 1 H), 7.23 (dd, J = 8.2, 0.7 Hz, 1 H), 5.99–5.83 (m, 1 H), 5.61–5.37 (m, 3 H), 4.91–4.79 (m, 1 H), 3.02 (dd, J = 13.3, 6.1 Hz, 1 H), 2.56 (dd, J = 13.3, 10.4 Hz, 1 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 151.0, 133.9, 132.2, 127.2, 126.8, 120.9, 120.4, 117.3, 112.5, 111.3, 69.7, 64.2, 42.1, 41.5 ppm. IR (film): ν = 1739, 1395, 1197, 1175, 1108, 1041, 885, 825 cm^–1; mp 176–178 °C. HRMS (ESI): m/z [M + Na⁺] calcd: 324.0413; found: 324.0417.