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Curtius rearrangement
Thermal or photochemical rearrangement of acyl azides into amines via isocy-anate intermediates. While the thermal rearrangement is a concerted process, the photochemical rearrangement goes through a nitrene intermediate.
The thermal rearrangement:
R Cl
O NaN3R N3
O '
R N C ON2nH2O
R NH2 CO2n
R Cl
O
R N
O
N3N NR N3
O
R Cl
N3O
'R N
O
N NN2n
R N C O
:OH2
H+
isocyanate intermediate
R NH2 CO2nRHN O
OH
:B
The photochemical rearrangement:
R N
O
N NN2n
hQ
R N:
O
nitrene
R N
OR N C O R NH2 CO2n
176
Example 19
O
O O
CO2MeHO2C DPPA, Et3N, t-BuOH
80 oC, 16 h, 64%
O
O O
CO2MeBocHN
Example 211
OOCO2H
EtO(CO)Cl, then NaN3EtOH, PhH, reflux, 55% OO
NHCO2Et
References
1. Curtius, T. Ber. Dtsch. Chem. Ges. 1890, 23, 3023. Theodor Curtius (18571928) was born in Duisburg, Germany. He studied music before switching to chemistry under Bunsen, Kolbe, and von Baeyer before succeeding Victor Meyer as a Professor of Chemistry at Heidelberg. He discovered diazoacetic ester, hydrazine, pyrazoline de-rivatives, and many nitrogen-heterocycles. Curtius also sang in concerts and com-posed music.
2. Chen, J. J.; Hinkley, J. M.; Wise, D. S.; Townsend, L. B. Synth. Commun. 1996, 26,617.
3. am Ende, D. J.; DeVries, K. M.; Clifford, P. J.; Brenek, S. J. Org. Process Res. Dev.1998, 2, 382.
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Lett. 2003, 44, 2745. 9. van Well, R. M.; Overkleeft, H. S.; van Boom, J. H.; Coop, A.; Wang, J. B.; Wang, H.;
van der Marel, G. A.; Overhand, M. Eur. J. Org. Chem. 2003, 1704. 10. Kedrowski, B. L. J. Org. Chem. 2003, 68, 5403. 11. Dussault, P. H.; Xu, C. Tetrahedron Lett. 2004, 45, 7455. 12. Holt, J.; Andreassen, T.; Bakke, J. M.; Fiksdahl, A. J. Heterocycl. Chem. 2005, 42,
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