Categories: C-N Bond Formation > Synthesis of azides >
Synthesis of acyl azides and related compounds
Recent Literature
Various carboxylic acids were converted into acyl azides in excellent yields in
the presence of trichloroacetonitrile, triphenylphosphine and sodium azide at
room temperature. The reaction allows the preparation of dipeptides without
deprotection or rearrangement during the reaction.
J.-G. Kim, D. O. Jang, Synlett, 2008,
2072-2074.
A general synthesis of acyl azides from the corresponding N-acyl
benzotriazoles affords acyl azides in good yields and avoids the use of acid
activators and NO+ equivalents typically employed to synthesize these
compounds from acid chlorides and hydrazides, respectively.
A. R. Katritzky, K. Widyan, K. Kirichenko, J. Org. Chem., 2007,
72, 5802-5804.
Amides react with NaN3 to give acyl azides in DMF at 25°C and
produce the symmetrical ureas in THF/H2O at 80 °C via a sequential
acyl substitution and Curtius rearrangement. All acyl azides were also obtained
from secondary amides via sequential reaction with p-toluenesulfonyl
chloride and NaN3. In addition, keto-stabilized iminophosphoranes can
also be prepared in a one-pot reaction.
D. Joseph, S. Lee, Org. Lett.,
2022, 24, 6186-6191.
A N-heterocyclic carbene catalyzes the oxidative esterification of various
aldehydes in the presence of 3,3',5'5-tetra-tert-butyldiphenoquinone to
yield hexafluoroisopropylesters, which are useful active esters for in situ
amide bond formation. This transition metal-free organocatalytic system also
enabled a mild oxidative azidation of aldehydes.
S. De Sarkar, A. Studer, Org. Lett., 2010,
12, 1992-1995.
Various aliphatic and aromatic aldehydes are converted into their corresponding
carbamoyl azides in very good yields in the presence of iodobenzene dichloride
and sodium azide in acetonitrile under nitrogen.
X.-Q. Li, X.-F. Zhao, C. Zhang, Synthesis, 2008,
2589-2593.
Aliphatic and aromatic aldehydes can be converted to acyl azides by
treatment with iodine azide. If the reaction is performed at reflux, Curtius rearrangement
occurs and carbamoyl azides are obtained directly from the aldehyde in good yield.
L. Marinescu, J. Thinggaard, I. B. Thomsen, M. Bols,
J. Org. Chem., 2003, 68, 9453-9455.
L. Marinescu, J. Thinggaard, I. B. Thomsen, M. Bols,
J. Org. Chem., 2003, 68, 9453-9455.
Aldehydes are safely and conveniently converted to acyl azides and benzyl
ethers to azido ethers by treatment with polymer supported iodine azide in MeCN
at 83 °C. The reaction provides an alternative to the use of iodine azide in
radical azidonations.
L. G. Marinescu, C. M. Pedersen, M. Bols, Tetrahedron, 2005,
61, 123-127.