NH-1,2,3-triazoles from azidomethyl pivalate and carbamates: Base-labile N-protecting groups

Synlett

Volumn , Issue 18, 2005, Pages 2847-2850

  Loren, Jon C ^a   Krasiński, Antoni ^a   Fokin, Valery V ^a   Sharpless, K Barry ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

Alkynes; Azides; Click chemistry; Cycloaddition; Heterocycles; Protecting groups; Triazoles

Indexed keywords

ALKYNE; AZIDE; CARBAMIC ACID DERIVATIVE; CARBOXYLIC ACID; SODIUM HYDROXIDE; TRIAZOLE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; CYCLOADDITION; ROOM TEMPERATURE;

EID: 27844570848     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2005-918944     Document Type: Article

References (21)

1. (a) Hartzel, L. W.; Benson, F. R. J. Am. Chem. Soc. 1954, 76, 667.
2. (b) Sheehan, J. C.; Robinson, C. A. J. Am. Chem. Soc. 1949, 71, 1436.
3. (c) Dimroth, O.; Fester, G. Ber. Dtsch. Chem. Ges. 1910, 43, 2219.
4. (a) Tanaka, Y.; Velen, S. R.; Miller, S. I. Tetrahedron 1973, 29, 3271.
5. (b) Tanaka, Y.; Miller, S. I. J. Org. Chem. 1973, 38, 2708.
6. (c) Woerner, F. P.; Reimlinger, H. Chem. Ber. 1970, 103, 1908.
7. Looker, J. J. J. Org. Chem. 1965, 30, 638.
8. Buckle, D. R.; Rockell, C. J. M. J. Chem. Soc., Perkin Trans. 1 1982,627.
9. Holzer, W.; Ruso, K. J. Heterocycl. Chem. 1992, 29, 1203.
10. Katritzky, A. R.; Zhang, Y.; Singh, S. Heterocycles 2003, 60, 1225.
11. (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. Ed. 2002, 41, 2596.
12. (b) Torrnøe, C. W.; Christensen, C.; Meldal, M. J. Org. Chem. 2002, 67, 3057.
13. Jin, T.; Kamijo, S.; Yamamoto, Y. Eur. J. Org. Chem. 2004, 3789.
14. Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. 2001, 40, 2004.
15. Suporting information (experimental procedures, yields and characterizations for compounds 4a-k, 5a-k, 6a-l) is available from the authors upon request. Aryl and alkyl alkyne groups (R′) are found in Table 1.
16. The ease of synthesis of N,N-disubstituted azidomethyl carbamate from secondary amines suggests that polymer-supported azidomethyl carbamates can be prepared and be converted to N-anchored triazoles. The latter would be cleavable under basic, rather than acidic conditions reported earlier. See: Harju, K.; Vahermo, M.; Mutikainen, I.; Yli-Kauhaluoma, J. J. Comb. Chem. 2003, 5, 826.
17. The pivaloyloxymethyl (POM) group, introduced by means of pivaloyloxymehtyl chloride, is a nitrogen-protecting group in nucleoside base chemistry. It was also used to a limited extent as a base-labile protecting group for nitrogen atoms in heterocycles such as imidazoles, tetrazoles, pyrroles and indoles. See: (a) Rasmussen, M.; Leonard, N. J. J. Am. Chem. Soc. 1967, 89, 5439.
18. (b) Araki, L.; Harusawa, S.; Yamaguchi, M.; Yonezawa, S.; Taniguchi, N.; Lilley, D. M. J.; Zhaob, Z.; Kuriharaa, T. Tetrahedron Lett. 2004, 45, 2657.
19. (c) Kalindjian, S. B.; Buck, I. M.; Davies, J. M. R.; Dunstone, D. J.; Hudson, M. L.; Low, C. M. R.; McDonald, I. M.; Pether, M. J.; Steel, K. I. M.; Tozer, M. J.; Vinter, J. G. J. Med. Chem. 1996, 39, 1806.
20. (d) Dhanak, D.; Reese, C. B. J. Chem. Soc., Perkin Trans. 1986, 1, 2181.
21. Azidomethyl N-tert-butyl carbamate was also studied. It is quantitatively removed from the 1,2,3-triazole nitrogen under conditions similar to the morpholine 4-carboxymethyl group. However N,N′-di-tert-butyl urea byproduct complicated product purification.