Abstract
2,4,6-Triazido-3,5-dichloropyridine was obtained in the reaction of pentachloropyridine with sodium azide. At room temperature, this azide reacts regioslectively with norbornene at the γ-azide group to give the corresponding 4-(3-azatricyclo[3.2.1.0]octanyl)-2,6-diazidopyridine in 88% yield. The cycloaddition of the dimethyl ester of acetylenedicarboxylic acid to this triazide proceeds at the azide groups at C(2) and C(6) in the pyridine ring to give 4-azido-2,6-di(4',5'-dimethoxycarbonyl)-1H-1,2,3-triazolopyridine. The analogous reaction of 2,4,6-triazido-3,5-dicyanopyridine with the dimethyl ester of acetylenedicarboxylic acid stops at the formation of 2,4-diazido-6-(4',5'-dimethoxycarbonyl)-1H-1,2,3-triazolopyridine. In contrast to reactions with electron-rich dipolarophiles, the cycloaddition of electron-deficient dipolarophiles to 2,4,6-triazidopyridines proceeds with thermodynamic control primarily a! t the azide groups bearing the highest orbital density in the HOMO.
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REFERENCES
S. V. Chapyshev and T. Ibata, Heterocycles, 36, 2185 (1993).
S. V. Chapyshev, Khim. Geterotsikl. Soedin., 1578 (1993).
S. V. Chapyshev, U. Bergstrasser, and M. Regitz, Khim. Geterotsikl. Soedin., 67 (1996).
S. V. Chapyshev and V. M. Anisimov, Khim. Geterotsikl. Soedin., 676 (1997).
S. V. Chapyshev and V. M. Anisimov, Khim. Geterotsikl. Soedin., 1521 (1997).
S. V. Chapyshev, Khim. Geterotsikl. Soedin., 1497 (2000).
T. Sasaki, S. Eguchi, M. Yamaguchi, and T. Esaki, J. Org. Chem., 46, 1800 (1981).
O. A. Radchenko, E. V. Proshakova, A. N. Kotlinskaya, and A. Ya. Il'chenko, Zh. Org. Khim., 27, 1463 (1991).
I. R. A. Bernard, G. E. Chivers, R. J. W. Cremlyn, and K. G. Mootoosamy, Aust. J. Chem., 27, 171 (1974).
R. A. Abramovitch, S. R. Challand, and Y. Yamada, J. Org. Chem., 40, 1541 (1975).
C. E. Pannell, US Patent 3,773,774 (1973); Chem. Abstr., 80, 59869 (1974).
C. E. Pannell, US Patent 3,883,542 (9175); Chem. Abstr., 83, 58670 (1975).
P. Bischof, Helv. Chim. Acta, 53, 1677 (1970).
H. Morrison, T. Singh, L. de Cardenas, and S. Severance, J. Am. Chem. Soc., 108, 3862 (1986).
J. J. P. Stewart, J. Comput. Chem., 10, 209 (1989).
SPARTAN Version 4.0, Wavefunction Inc., 18401 Von Karman Ave.,#370 Irvine; Chem. Abstr., 92715 (1995).
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Chapyshev, S.V. Regioselective Cycloaddition of the Dimethyl Ester of Acetylenedicarboxylic Acid to 2,4,6-Triazidopyridines. Chemistry of Heterocyclic Compounds 37, 861–866 (2001). https://doi.org/10.1023/A:1012451508449
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DOI: https://doi.org/10.1023/A:1012451508449