N-carboalkoxy-2-nitrobenzenesulfonamides: A practical preparation of N- Boc-, N-Alloc-, and N-Cbz-protected primary amines

Synlett

Volumn , Issue 8, 1999, Pages 1301-1303

  Fukuyama, Tohru ^a,c   Cheung, Mui ^b   Kan, Toshiyuki ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b RICE UNIVERSITY   (United States)

^c GLAXOSMITHKLINE   (United States)

Author keywords

Alkylation; Deprotection; Mitsunobu conditions; N carboalkoxy 2 nitrobenzenesulfonamides; Primary amines

Indexed keywords

2 NITROBENZENESULFONAMIDE DERIVATIVE; AMINE; BENZENESULFONAMIDE DERIVATIVE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; ORGANIC CHEMISTRY; REACTION ANALYSIS; SYNTHESIS;

EID: 0032769782     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2827     Document Type: Article

References (11)

1. For a review of the Gabriel synthesis, see: Gibson, M. S.; Bradshaw, R. W. Angew. Chem., Int. Ed. Engl. 1968, 7, 919.
2. For a review of the Gabriel synthesis, see: Gibson, M. S.; Bradshaw, R. W. Angew. Chem., Int. Ed. Engl. 1968, 7, 919.
3. Henry, J. R, Marcin, L. R., McIntosh, M. C., Scola, P. M., Harris, G. D., Weinreb, S. M. Tetrahedron Lett. 1989, 30, 5709.
4. (a) Mitsunobu, O. Synthesis 1981, 1.
5. (b) Hughes, D. L. Org. React. 1992, 42, 335.
6. Tsunoda, T.; Yamamoto, H.; Goda, K.; Ito, S. Tetrahedron Lett. 1996, 37, 2457.
7. (a) Fukuyama, T.; Jow, C.-K.; Cheung, M. Tetrahedron Lett. 1995, 36, 6373.
8. (b) Fukuyama, T.; Cheung, M.; Jow, C.-K.; Hidai, Y.; Kan, T. Tetrahedron Lett. 1997, 38, 5831.
9. For this protocol, 2,4-dinitrobenzenesulfonamide is also as useful as 2-nitrobenzenesulfonamide (1), with the exception of poor alkylaling agents such as heptyl bromide. Upon prolonged exposure to basic conditions, extensive decomposition of 2,4-dinitrobenzenesulfonamide was observed. For the deprotection of the Alloc group in the presence of 2,4-dinitrobenzenesulfonamides, dimedone was used as a nucleophile to avoid the pyrrolidine-induced deprotection of the sulfoneamides.
10. 2O at 23 °C. After 25 min the reaction mixture was filtered through Celite pad and washed with AcOEt. The filtrate was evaporated and triturated with 40% ether in hexanes to give 2,4-dinitrobenzenesulfonamide as a yellow solid (97%).
11. Satisfactory spectroscopic data were obtained on all new compounds.