T. Gasperi et al. / Tetrahedron Letters 44 (2003) 4953–4956
4955
General procedure. For compounds 3 and 6c. To a stirred
solution of the substrate 2 (10.2 mmol) in 2.0 mL of
CH2Cl2, NsONHCO2Et (10.2 mmol, 1 equiv.) and CaO
were added every hour, reaching the molar ratio sub-
strate:NsONHCO2Et:CaO reported in Table 1. Because
the reaction is exothermic, during the addition the flask
was cooled in a water bath to avoid overheating. After
6 h, 10 mL of hexane was added. After filtration, the
organic mixture containing the aziridine 3 was concen-
trated in vacuo. The product was isolated by flash
chromatography on silica gel (hexane:ethyl acetate) in
the yields reported in Table 1.
12. (a) Lee, K.; Jackson, J. A.; Wiemer, D. F. J. Org. Chem.
1993, 58, 5967–5971; (b) Rambaud, M.; Del Vecchio, A.;
Villieras, J. Synth. Commun. 1984, 833–841.
13. (a) Beji, F.; Besbes, R.; Amri, H. Synth. Commun. 2000,
21, 3947–3954; (b) Minami, T.; Niki, I.; Agawa, T. J.
Org. Chem. 1974, 39, 3236–3238; (c) Henning, R.; Hoff-
mann, H. M. R. Tetrahedron Lett. 1982, 23, 2305–2308.
1
14. Spectral data: 3a: H NMR (200 MHz, CDCl3): l 1.26 (t,
3H, CH2CH3); 2.51 (d, 1H, CHN, J=1.2 Hz); 2.38–2.67
(m, 2H, OCH2CH2); 2.81 (d, 1H, CHN, J=1.2 Hz); 4.18
(q, 2H, CH2CH3); 4.43–4.65 (m, 2H, OCH2CH2); 13C
NMR (50 MHz, CDCl3): 14.2, 26.8, 36.3, 42.0, 63.1, 65.6,
159.9, 172.8; IR: (CCl4): 1794, 1748 cm−1; GC–MS: m/z
1
For compounds 4: The aziridines 3 were stirred at 80°C
in the presence of acetic acid as a solvent. Different
substrates needed different heating times to reach the
complete conversion.18 The reaction mixture was evap-
orated under reduced pressure, and then CHCl3 was
added. The organic layer was washed with a saturated
solution of NaHCO3 then dried over Na2SO4. After the
work-up, the solvent was evaporated in vacuo giving
the products 4.19
185 [M+] (<1%), 69 (100%). 3b: H NMR: l 1.21 (t, 3H,
CH2CH3); 1.29 (d, 3H, CHCH3, J=5.6 Hz); 2.31–2.43
(m, 2H, OCH2CH2); 2.95 (q, 1H, CHN, J=5.6 Hz); 4.12
(q, 2H, CH2CH3); 4.36–4.64 (m, 2H, OCH2CH2); 13C
NMR: 14.1, 14.2, 24.1, 42.0, 45.8, 62.7, 65.7, 159.9, 173.0;
IR: 1785, 1749 cm−1; GC–MS: m/z 199 [M+] (<1%), 54
1
(100%). 3c: H NMR: l 1.25 (t, 3H, CH2CH3); 1.20–1.64
(m, 11H, CH2(CH2)3CH3); 2.26–2.34 (m, 2H, OCH2CH2);
2.91 (t, 1H, CHN, J=5.6 Hz); 4.17 (q, 2H, OCH2CH3);
4.37–4.67 (m, 2H, OCH2CH2); 13C NMR: 13.8, 14.1,
22.1, 24.4, 26.4, 29.0, 31.1, 45.8, 46.7, 62.7, 65.0, 65.7,
159.9, 173.0; IR: 1790, 1735 cm−1 GC–MS: m/z 255 [M+]
(7.2%), 55 (100%). 3d: 1H NMR: l 1.29 (t, 3H, CH2CH3);
1.97 (ddd, 1H, OCH2CHH, J=5.0, 8.6, 14.0 Hz); 2.44
(ddd, 1H, OCH2CHH, J=7.0, 9.2, 14.0 Hz); 4.05 (s, 1H,
CHN); 4.25 (q, 2H, CH2CH3); 4.21–4.40 (m, 1H,
OCHHCH2); 4.57 (ddd, 1H, OCHHCH2, J=5.0, 9.2, 9.2
Hz); 7.27–7.44 (m, 5H, CH arom.); 13C NMR: 14.2, 23.8,
48.6, 48.7, 63.2, 65.6, 127.1, 128.6, 128.7, 132.9, 159.5,
172.2; IR: 1785, 1735 cm−1 GC–MS: m/z 261 [M+] (<1%),
Acknowledgements
We thank the Italian Ministero dell’Istruzione dell’Uni-
versita` e della Ricerca (MIUR), the University ‘La
Sapienza’ of Rome (National Project ‘Stereoselezione in
Sintesi Organica. Metodologie e Applicazioni’) and
Consiglio Nazionale delle Ricerche (CNR) for financial
support.
1
173 (100%). 3e: H NMR: 1.23 (t, 3H, CH2CH3); 1.35 (s,
3H, CCH3); 1.55 (s, 3H, CCH3); 2.33 (ddd, 1H,
OCH2CHH, J=4.7, 8.1, 13.8 Hz); 2.50–2.67 (m, 1H,
OCH2CHH); 4.14 (q, 2H, CH2CH3); 4.18–4.40 (m, 1H,
OCHHCH2); 4.50 (ddd, 1H, OCHHCH2, J=4.7, 9.0, 9.0
Hz); 13C NMR: 14.3, 16.4, 22.4, 25.1, 47.5, 48.3, 62.2,
64.6, 157.8, 171.7; IR: 1781, 1730 cm−1 GC–MS: m/z 213
[M+] (<1%), 140 (100%). 3f: 1H NMR: 1.28 (t, 3H,
CH2CH3); 1.49 (d, 3H, CHCH3, J=5.7 Hz); 2.17 (ddd,
1H, OCH2CHH, J=3.4, 7.3, 13.5, Hz); 2.73–2.90 (m, 1H,
OCH2CHH); 2.87 (q, 1H, CHCH3, J=5.7 Hz); 4.19 (q,
2H, CH2CH3); 4.42 (ddd, 1H, OCHHCH2, J=7.3, 9.2,
9.2 Hz); 4.56 (ddd, 1H, OCHHCH2, J=3.4, 9.2, 9.2 Hz);
13C NMR: 11.6, 14.3, 26.4, 44.6, 45.1, 62.8, 65.0, 159.1,
171.3; IR: 1788, 1723 cm−1; GC–MS: m/z 199 [M+]
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