Triazenes: A useful protecting strategy for sensitive secondary amines

Synlett

Volumn , Issue 8, 1999, Pages 1304-1306

  Lazny, Ryszard ^a   Poplawski, Janusz ^a   Köbberling, Johannes ^b   Enders, Dieter ^b   Bräse, Stefan ^b  

^a UNIVERSITY OF BIALYSTOK   (Poland)

^b RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

Amines; Piperidones; Protecting groups; Triazenes

Indexed keywords

AMINE; PIPERIDONE DERIVATIVE; TRIAZENE DERIVATIVE;

ALKYLATION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CRYSTALLIZATION; ORGANIC CHEMISTRY; OXIDATION REDUCTION REACTION; SYNTHESIS;

EID: 0032792705     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2803     Document Type: Article

References (18)

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2. Kocienski, P. J. Protecting Groups; Thieme Verlag Stuttgart: 1994, p. 195-199.
3. For the use of triazenes as a linker in SPOS, see: Bräse, S.; Köbberling, J.; Enders, D.; Lazny, R.; Wang, M.; Brandtner, S.; Tetrahedron Lett. 1999, 40, 2105-2108.
4. Stevens, M. F. G.; Philipp, K. S., Rathbone, D. L.; O'Shea, D.M.; Queener, S. F. J. Med. Chem. 1997, 40, 1886-1893.
5. Gross, M. L.; Blank, D. H.; Welch, W. M. J. Org. Chem. 1993, 58, 2104-2109.
6. Nicolaou, K. C.; Boddy, C. N. C.; Natarajan, S.; Yue, T. Y.; Li, H.; Bräse, S.; Ramanjulu, J. M. J. Am. Chem. Soc. 1997, 119, 3421-3422.
7. Nicolaou K. C.; Takayanagi, M., Jain, N. F.; Natarajan, S.; Koumbis, A. E.; Bando, T.; Ramanjulu, J. M. Angew. Chem. 1998, 110, 2881-2883.
8. For recent publication on bistriazenes and triazenes see: Hooper, D. L.; Pottier, I. R.; Vacheresse, M.; Vaughan, K. Can. J. Chem. 1998, 76, 125.
9. Bräse, S.; Enders, D.; Köbberling, J.; Avemaria, F. Angew. Chem. 1998; 110, 3614-3616; Angew. Chem. Int. Ed. Engl. 1998, 57, 3413-3415.
10. Bräse, S.; Enders, D.; Köbberling, J.; Avemaria, F. Angew. Chem. 1998; 110, 3614-3616; Angew. Chem. Int. Ed. Engl. 1998, 57, 3413-3415.
11. CAUTION: Triazenes are potential carcinogenic and some members are reported to be active towards biological systems. Therefore we recommend special caution during handling.
12. Gescher, A.; Turnbull, C. P.; Stevens M. F. G. J. Chem. Soc. Perkin Trans. I 1977, 2078-2082.
13. 1H NMR: 2.44 (d, 3 H), 2.48-2.57 (m, 2 H), 2.58-2.70 (m, 2 H), 7.18-7.45 (m, 4 H), 7.80-7.90 (m, 1 H).
14. Lyle, R. E.; Maloney, J. R.; White, R. J. Org. Prep. Proced. 1980, 12, 255.
15. Corcy, E. J.; Knapp, S. Tetrahedron Lett. 1976, 3667 and 4687.
16. 2O
17. Strict exclusion of moisture is not necessary. Water reacts with acid chlorides yielding the corresponding acid and as well as HCl. Both acids increase the cleavage rate of the triazene prior to acylation rather than disturbing the reaction sequence.
18. Typical procedure for the deprotection of amines and in situ acylation: To a cooled (0 °C) solution of the triazene in dichloromethane (1.0 mmol), the acid chloride (4.0 mmol, 4 equivalents) was added. After 24 h, the excess of acid chloride and the solvent were removed under vacuum.