Highly diastereoselective aziridination of α,β-unsaturated amides using diaziridine

Chemistry Letters

Volumn , Issue 10, 2001, Pages 984-985

  Ishihara, Hiroyuki ^a   Ito, Yoshio N ^a   Katsuki, Tsutomu ^a  

^a KYUSHU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0035541295     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2001.984     Document Type: Article

References (8)

1. K. Hori, H. Sugihara, Y. N. Ito, and T. Katsuki, Tetrahedron Lett., 40, 5207 (1999).
2. After we published the original paper (Reference 1) on cis-selective aziridination, we found that chemical yields of cis-aziridines were remarkably improved by optimizing reaction temperature. The results should be published elsewhere.
3. Diaziridine 2 was prepared from cyclohexanecarbaldehyde, methylamine, and chloramine according to the reported method. E. Schmitz, Chem. Ber., 95, 688 (1962).
4. 2. Extraction and column chromatography on basic silica gel (Fuji Silysia Chemical Ltd., NH-DM1020, hexane-AcOEt 4:1-3:7) afforded the corresponding trans-aziridine as colorless crystals (32.0 mg, 74%).
5. The stereochemistry of the aziridine obtained from 10 was confirmed to be 2,3-trans by measuring NOESY. The tarns-isomer showed NOE between 2- and 3-methyl groups.
6. (Formula presented) The other 2,3-disubstituted aziridine products were assigned to be trans based on the coupling constants of hydrogens at C2 and C3 of the aziridines.
7. Diaziridine 12 was prepared by the method employed for the preparation of 2 (Reference 3). The relative stereochemistry of 12 was not asgined though 12 was single diastereomer.
8. The stereochemistry of the product was determined by the following chemical correlation. Tosylation with tosyl chloride and triethylamine and the subsequent hydrogenolysis with hydrogen and palladium on carbon afforded N-(N-tosylphenylalanyl)pyrrolidine, which showed identical NMR spectra and retention time in HPLC analysis using chiral stationary phase column with the compound prepared from (S)-phenylalanine.