Stereospecfic Synthesis of Trans-1-benzyl-2-ethoxycarbonyl-3-phenyl Aziridine

References

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• Ploux , O. , Caruso , M. , Chassaig , G. and Marquet , A. 1988 . J. Org. Chem. , 53 : 3154 In general, the formation of the aziridine carboxylate from α,β-dibromo compounds is not stereospecific, see for example
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• A mixture of trans ethyl glycidate (5 g, 0.026 mol), benzylamine(7ml), saturated NH4Cl (4 ml) in ethanol (30 ml) was heated at 80°C for 5 h. After cooling, the reaction mixture was diluted with Et20 and sat. NaHCO3 was added. The solution was filtered through a pad of Celite (EtOAc rinse), dried, and concentrated. The crude product was purified by column chromatography (20% EtOAc - petrol, SiO2) to give 1 as a colorless oil (5.0 g, 64%) which solidified on standing, mp 52–54°C. 1R (neat) 1731 cm-1, 1H NMR (CDCl3) 1.1 (t, 3H), 2.2 (broad S, 1H), 3.2 (d, 1H), 3.7 (q, 2H), 4.1 (m, 2H), 4.5 (t, 1H), 7.3 (m, 10H). Anal. Calcd. for C18H21O3N: C, 72.22, H, 7.07, N, 4.68. Found: C, 72.27, H, 7.23, N, 4.67
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• a. The regiochemistry of the product was confirmed by a comparison with its corresponding regioisomer prepared from phenylserine and benzaldehyde via a reductive amination reaction with NaCNBH3in methanol.b. About 10% yield of the corresponding benzylamide of 1 was also isolated
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• To a solution of 1 (0.47 mg, 0.00158 mmol) and Ph3P (0.62 g, 0.00237 mol) in THF (3 ml) at 0°C was added a solution of diethyl azodicarboxylate (0.37 ml, 0.00237 mol) in THF (2 ml) dropwise. The solution was stirred at 0°C for 1 h and then stirred at r.t. for 10 h. Concentration and purification of the crude product by column chromatography (20% EtOAc-petrol, SiO2) gave the trans aziridine 2 (0.29 g, 65%) as a colorless oil. IR (film) 1727 cm-1, 1H NMR (CDCl3) 1.1 (t, 3H), 2.8 (broad d, J= 2Hz, 1H), 3.1 (broad d, J= 2Hz, 1H), 4.1 (m, 4H), 7.1 (m, 10H), HRMS: (C18H19NO2) calcd: 281.1416. Found: 281.1426
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• Batterham , T. J. 1973 . NMR spectra of Simple Heterocycles , 137 – 140 . New York : John Wiley & Sons . trans aziridine ring protons: J = 2.0–2.7 Hz, cis aziridine ring protons: J = 5.0–6.0 Hz.b. The cis-aziridine 3 was prepared according to the reported procedure6
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