cis-selective aziridination of cis- or trans-α,β-unsaturated amides using diaziridine

Tetrahedron Letters

Volumn 40, Issue 28, 1999, Pages 5207-5210

  Hori, Kiyoto ^a   Sugihara, Hiroyasu ^a   Ito, Yoshio N ^a   Katsuki, Tsutomu ^a  

^a KYUSHU UNIVERSITY   (Japan)

Author keywords

Amides; Aziridines; Diastereoselection; Diaziridines

Indexed keywords

AMIDE; AZIRIDINE DERIVATIVE;

ARTICLE; AZIRIDINATION; MOLECULAR INTERACTION; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033538603     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00939-9     Document Type: Article

References (17)

1. Vasella, A.; Witzig, C.; Husi, R. Helv. Chim. Acta 1991, 74, 1362.
2. In heteroatom transfer reaction, the heteroatom works both as a nucleophile and an electrophile.
3. Schmitz, E.; Ohme, R. Org. Syn. 1973, Coll. Vol. V, 897.
4. Typical experiment is as follows. A solution of n-butyllithium in hexane (1.6 mol/l, 0.254 ml, 0.40 mmol) was added to a solution of 1 (44.8 mg, 0.40 mmol) in THF (4 ml) at -78 °C. A THF solution of 2a (27.8 mg, 0.20 mmol) was added to the mixture at the same temperature and the mixture was allowed to warm to rt. After stirring for 1 d at rt, the mixture was diluted with water. Extraction and column chromatography on basic silica gel (Fuji Silysia Chemical Ltd., NH-DM1020, hexane-AcOEt 4:1-7:3) afforded 3a as a colorless oil ( 25.2 mg, 82 %).
5. 2 were also reported. Vedejs E.; Sano, H. Tetrahedron Lett. 1992, 33, 3261 and references cited therein.
6. 2 were also reported. Vedejs E.; Sano, H. Tetrahedron Lett. 1992, 33, 3261 and references cited therein.
7. 2 were also reported. Vedejs E.; Sano, H. Tetrahedron Lett. 1992, 33, 3261 and references cited therein.
8. 2 were also reported. Vedejs E.; Sano, H. Tetrahedron Lett. 1992, 33, 3261 and references cited therein.
9. 2 were also reported. Vedejs E.; Sano, H. Tetrahedron Lett. 1992, 33, 3261 and references cited therein.
10. 2R; Fioravanti, S.; Pellacani, L.; Stabile, S.; Tardella, P. A.; Ballini, R. Tetrahedron Lett. 1997, 38, 3309. See also Tamura, Y.; Minamikawa, J.; Ikeda, M. Synthesis 1977, 1.
11. 2R; Fioravanti, S.; Pellacani, L.; Stabile, S.; Tardella, P. A.; Ballini, R. Tetrahedron Lett. 1997, 38, 3309. See also Tamura, Y.; Minamikawa, J.; Ikeda, M. Synthesis 1977, 1.
12. 2R; Fioravanti, S.; Pellacani, L.; Stabile, S.; Tardella, P. A.; Ballini, R. Tetrahedron Lett. 1997, 38, 3309. See also Tamura, Y.; Minamikawa, J.; Ikeda, M. Synthesis 1977, 1.
13. 2R; Fioravanti, S.; Pellacani, L.; Stabile, S.; Tardella, P. A.; Ballini, R. Tetrahedron Lett. 1997, 38, 3309. See also Tamura, Y.; Minamikawa, J.; Ikeda, M. Synthesis 1977, 1.
14. The reaction of 3a with p-toluenesulfonyl chloride gave 4 in 90% yield. Authentic samples of 4 and 5 were prepared by amidolysis of the corresponding methyl esters as shown in the following scheme, cis-Aziridine methyl ester was prepared from threonine. Funaki, I.; Bell, R. P. L.; Thijs, L.; Zwanenburg, B. Tetrahedron 1996, 52, 12253.
15. The reaction of 3a with p-toluenesulfonyl chloride gave 4 in 90% yield. Authentic samples of 4 and 5 were prepared by amidolysis of the corresponding methyl esters as shown in the following scheme, cis-Aziridine methyl ester was prepared from threonine. Funaki, I.; Bell, R. P. L.; Thijs, L.; Zwanenburg, B. Tetrahedron 1996, 52, 12253.trans-Aziridine methyl ester was prepared from methyl crotonate. Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Org. Chem. 1991, 56, 6744.
16. These reactions were conducted at a temperature below -25 °C for one day. Satisfactory H NMR spectra were observed for every aziridine product.
17. The present reaction is in a striking contrast to the trans-selective aziridination using methoxyamine (reference 6). Relative stability of trans- and cis-3-methyl-2-vinylaziridines has been reported. Ibuka, T.; Mimura, N.; Aoyama, H.; Akaji, M.; Ohno, H.; Miwa, Y.; Taga, T.; Nakai, K.; Tamamura, H.; Fujii, N.; Yamamoto Y. J. Org. Chem. 1997, 62, 999.