Palladium-Catalyzed Reaction of Bicyclic Hydrazines with Allyl- and Arylstannanes in Ionic Liquid [bmim]PF₆: A Facile Method for the Synthesis of Substituted Hydrazinocyclopentene Derivatives

Abstract

A method for the synthesis of substituted hydrazinocyclopentenes by the palladium-catalyzed reaction of azabicyclic and tricyclic olefins with organostannanes is described. The reaction is facile with catalytic amount of Lewis acid and the rate of the reaction is enhanced by the use of ionic liquid, [bmim]PF₆ as solvent.

Key words

bicyclic hydrazines - disubstituted cyclopentenes - ionic liquid [bmim]PF₆ - allyltri-n-butyltin - Lewis acids - palladium catalyst

References

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15

Spectral Data for 4: R _f = 0.35 (30% EtOAc-hexane). IR (neat): ν_max = 3294, 3057, 2979, 2923, 1713, 1517, 1414, 1295, 1239, 1125, 1063, 909, 759, 713 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 6.52 (s, 1 H), 5.72-5.86 (m, 1 H), 5.59-5.63 (m, 2 H), 4.99-5.09 (m, 2 H), 4.55-4.57 (m, 1 H), 4.19 (q, 4 H), 2.85 (br s, 1 H), 2.31-2.53 (m, 3 H), 2.10-2.17 (m, 1 H), 1.27 (t, 6 H). ¹³C NMR (75 MHz, CDCl₃): δ = 156.71, 155.94, 136.38, 132.82, 128.45, 116.25, 63.08, 62.35, 61.95, 47.62, 37.55, 35.17, 14.53, 14.46. LRMS (FAB): m/z calcd for C₁₄H₂₂N₂O₄ [M + 1]: 283.1658; found: 283.1666 [M + 1]. Anal. Calcd for C₁₄H₂₂N₂O₄: C, 59.56; H, 7.85; N, 9.92. Found: C, 59.86; H, 7.89; N, 10.18.
Data for 7: R _f = 0.39 (60% EtOAc-hexane). IR (neat): ν_max = 3433, 3175, 3067, 2954, 2923, 2851, 1769, 1697, 1604, 1506, 1429, 1249, 1130, 914, 770, 708 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 9.22 (br s, 1 H), 7.37-7.75 (m, 5 H), 5.73-5.75 (m, 1 H), 5.66-5.69 (m, 2 H), 5.02-5.11 (m, 2 H), 4.58-4.61 (m, 1 H), 2.89-2.90 (m, 1 H), 2.69-2.70 (m, 1 H), 2.48-2.49 (m, 1 H), 2.16-2.26 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 153.70, 151.65, 135.15, 132.72, 131.28, 128.84, 128.30, 127.90, 125.27, 117.05, 115.93, 59.75, 48.43, 37.62, 35.35. MS (LR-FAB): m/z calcd for C₁₆H₁₇N₃O₂ [M + 1]: 284.1399; found: 284.6529 [M + 1].
Data for 13: R _f = 0.67 (25% EtOAc-hexane). IR (neat):
ν_max = 3298, 2985, 2918, 1717, 1069, 914, 781 cm^-1.
¹H NMR (300 MHz, CDCl₃): δ = 7.22-7.28 (m, 5 H), 6.68 (br s, 1 H), 5.85-5.87 (m, 1 H), 5.69-5.71 (m, 1 H), 4.73-4.76 (m, 1 H), 4.18-4.25 (q, 4 H), 4.01 (br s, 1 H), 2.61-2.67 (m, 2 H), 1.29 (t, 6 H). ¹³C NMR (75 MHz, CDCl₃):
δ = 156.82, 156.21, 132.71, 129.71, 128.38, 127.47, 126.47, 67.32, 62.29, 62.06, 53.76, 35.15, 14.43, 14.19. MS (LR-FAB): m/z calcd for C₁₇H₂₂N₂O₄: 318.1580. Found: 318.6929.