A General Procedure for theOne-pot Preparation of Polyfunctionalized Nitrocyclopropanes

Abstract

Nitrocyclopropane formation has been successfully carried outby reaction of bromonitromethane with electrophilic alkenes bearingtwo electron-withdrawing groups in the α- and β-positions,and in the presence of potassium carbonate as base. The method allowsgood yields and moderate to satisfactory diastereoselectivity withlinear alkenes, while shows the complete formation of the exo-product with N-alkylmaleimides.

nitrocyclopropanes - bromonitromethane - potassium carbonate - one-pot preparation - Michael reaction

References

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11

Selected analytical data for the compounds 3h-j. 3h: White solid, mp 132-134 °C.IR: 1710, 1552 cm^-1; ¹HNMR (CDCl₃): δ = 2.92 (s, 3 H), 3.39(d, 2 H, J = 1.4 Hz), 4.65 (t, 1H, J = 1.6 Hz); ¹³CNMR (CDCl₃): δ = 25.1, 27.7, 62.6, 168.9;EIMS (70 eV) m/z: 170 (M⁺),96, 39. Anal. Calcd. For C₆H₆N₂O₄ (170.12):C, 42.36; H, 3.55; N, 16.47. Found: C, 42.52; H, 3.64; N, 16.38. 3i: White solid, mp 124-126 °C. IR:1716, 1547 cm^-1; ¹HNMR (CDCl₃): δ = 1.14 (t, 3 H, J = 7.2 Hz), 3.38 (d, 2 H, J = 1.5 Hz), 3.48 (q, 2 H, J = 7.3 Hz), 4.59 (t, 1 H, J = 1.6 Hz); ¹³CNMR (CDCl₃): δ = 13.0, 27.6, 34.2,62.6, 168.6; EIMS (70 eV) m/z:184 (M⁺), 169, 95, 39. Anal. Calcd For C₇H₈N₂O₄ (184.15):C, 45.66; H, 4.38; N, 15.21. Found: C, 45.55; H, 4.46; N, 15.14. 3j: White solid, mp 158-160 °C.IR: 1709, 1557 cm^-1; ¹HNMR (CDCl₃):
δ = 1.50 (s,9 H), 3.25 (d, 2 H, J = 1.4Hz), 4.51 (t, 1 H, J = 1.4 Hz); ¹³CNMR (CD₃COCD₃): δ = 29.5,29.9, 30.3, 63.1, 171.2; EIMS (70 eV) m/z:212 (M⁺), 197, 157, 95, 56, 39. Anal. CalcdFor C₉H₁₂N₂O₄ (212.20):C, 50.94; H, 5.79; N, 13.20. Found: C, 60.06; H, 5.59; N, 13.11.