Nickel(0)-Catalyzed [3+2]-Cycloadditions of Bis(alkylidenecyclopropanes) with Diazenes: A Facile Synthesis of Functionalized ­Pyrazolidine-1,2-dicarboxylates

Abstract

A nickel(0)-catalyzed intermolecular [3+2] cycloaddition of bis(alkylidenecyclopropanes) with diazenes such as diethyl or diisopropyl azodicarboxylate gave pyrazolidine-1,2-dicarboxylates in moderate to good yields (61–72%).

Keywords

bisalkylidenecyclopropanes - diazenes - pyrazolidine­dicarboxylates - [3+2]-cycloaddition - nickel catalysis

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• 17 [3+2]-Cycloadducts 3a–f; General Procedure Dialkyl azodicarboxylate 2 (2 mmol, 10 equiv) was added to a solution of the appropriate bis(alkylidenecyclopropane) 1 (0.2 mmol, 1 equiv) in toluene (4 mL), and the mixture was degassed for 10 min under argon. Ni(COD)₂ (5 mol%) was added, and the mixture was heated to 90 °C for 16 h. After completion of the reaction, the mixture was cooled to r.t., directly loaded onto a column without evaporation, and purified by flash chromatography [silica gel (100–200 mesh), EtOAc–hexanes].
• 18 Diethyl (3E)-3-[5-Cyclopropylidene-3,3-bis(methoxycarbonyl)pentylidene]pyrazolidine-1,2-dicarboxylate (3a) Colorless liquid; yield: 119 mg (72%). ¹H NMR (300 MHz, CDCl₃): δ = 5.71 (m, 1 H), 5.48 (m, 1 H), 4.13–4.20 (m, 4 H), 3.71 (s, 6 H), 3.65 (m, 2 H), 2.75 (d, J = 9, Hz, 2 H), 2.49 (br s, 2 H), 2.01 (m, 2 H), 1.22–1.27 (m, 6 H), 0.99 (m, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 171.1, 156.3, 137.7, 126.9, 116.0, 112.3, 61.5, 57.7, 52.1, 46.7, 37.0, 35.5, 29.3, 14.6, 2.6, 2.0. LRMS (ESI): m/z = 439.2 [M + H]⁺. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₁H₃₁N₂O₈: 439.2080; found: 439.2067. Diethyl (3E)-3-[5-Cyclopropylidene-3,3-bis(isopropoxycarbonyl)pentylidene]pyrazolidine-1,2-dicarboxylate (3c) Pale-yellow liquid; yield: 94 mg (61%). ¹H NMR (300 MHz, CDCl₃): δ = 5.61 (m, 1 H), 5.57 (m, 1 H), 5.03 (m, 2 H), 4.19 (m, 4 H), 3.70 (m, 2 H), 2.76 (d, J = 7.2 Hz, 2 H), 2.66 (bs, 2 H), 1.78 (m, 2 H), 1.20–1.32 (m, 18 H), 1.05 (t, J = 4.5 Hz, 2 H), 1.02 (t, J = 4.5 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 170.4, 155.6, 137.7, 126.2, 115.5, 112.1, 69.0, 62.4, 57.0, 46.1, 37.8, 35.8, 29.6, 21.5, 14.5, 2.8, 2.0. LRMS (ESI): m/z = 495.3 [M + H]⁺. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₅H₃₉N₂O₈: 495.2706; found: 495.2718.