[CH:1]([CH:3]1[CH2:5][CH:4]1C(O)=O)=[CH2:2].C([N:11]([CH2:14]C)CC)C.C1([O:22]P(N=[N+]=[N-])(OC2C=CC=CC=2)=O)C=CC=CC=1.[C:35]([OH:39])([CH3:38])([CH3:37])[CH3:36]>C1(C)C=CC=CC=1>[C:35]([O:39][C:14]([NH:11][CH:4]1[CH2:5][CH:3]1[CH:1]=[CH2:2])=[O:22])([CH3:38])([CH3:37])[CH3:36]
2-Ethenylcyclopropanecarboxylic acid (14.42 g, 129 mmol) from Step B was dissolved in 100 mL of toluene at 0° C. Triethyl amine (19.79 mL) was added in one portion, followed by 30.5 mL of diphenylphosphonoazide (DPPA) added dropwise from an addition funnel. After the addition of DPPA was complete the reaction mixture was warmed to 70° C. and stirred at 70° C. for 45 minutes. tert-Butyl alcohol (50 mL) was added in one portion to the reaction mixture. The temperature of the reaction mixture was then raised to 100° C. and it was stirred overnight at this temperature. TLC analysis (on silica gel plates eluted with 25% ethyl acetate in hexane) showed no remaining starting material. The reaction mixture was diluted with 150 mL of methylene chloride, washed with 100 mL of 1M aqueous phosphoric acid solution, 100 mL of saturated sodium bicarbonate solution and 100 mL of saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel eluted with 5% ethyl acetate in hexane. N-tert-Butoxycarbonyl-2-ethenylcyclopropylamine was obtained in 38% yield (8.97 g) as a clear colorless oil. 1H NMR (CDCl3) 0.90 (m, 2H), 1.45 (s, 9H), 1.5 (m, 1H), 2.50 (m, 1H), 4.97 (dd, 1H), 5.07 (dd, 1H), 5.51 (m, 1H).
Wird geladen…
