Categories: N/N Bond Formation >
Synthesis of Azides
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Imidazole-1-sulfonyl azide hydrochloride equals triflyl azide in its ability to
act as a “diazo donor” in the conversion of both primary amines into azides and
activated methylene substrates into diazo compounds. Crucially, this reagent can
be prepared in a one-pot reaction on a large scale from inexpensive materials,
is shelf-stable and is conveniently crystalline.
E. D. Goddard-Borger, R. V. Stick, Org. Lett., 2007,
9, 3797-3800.
The synthesis of aromatic azides from the corresponding amines is
accomplished under mild conditions with tert-butyl nitrite and
azidotrimethylsilane. 1,4-Disubstituted 1,2,3-triazoles were obtained in
excellent yields from various aromatic amines without the need for isolation of
the azide intermediates.
K. Barral, A. D. Moorhouse, J. E. Moses, Org. Lett., 2007,
9, 1809-1811.
Aliphatic and aromatic aldehydes
gave acyl azides by reaction with iodine azide at 0 - 25°C. If the reaction
is performed at reflux Curtius rearrangement occurs and carbamoyl azides are
obtained directly from the aldehyde in 70-97% yield.
L. Marinescu, J. Thinggaard, I. B. Thomsen, M. Bols,
J. Org. Chem., 2003, 68, 9453-9455.
Stable and easy to handle imidazole-1-sulfonyl azide hydrogen sulfate is an
efficient reagent for the synthesis of sulfonyl azides from primary sulfonamides
in an experimentally simple and high-yielding method without Cu salts.
Furthermore, 15N NMR mechanistic studies show the reaction proceeds
via a diazo transfer mechanism.
M. Y. Stevens R. T. Sawant, L. R. Odell, J. Org. Chem., 2014,
79, 4826-4831.
Triflyl azide serves as an efficient diazo transfer reagent in a direct
synthesis of sulfonyl azide building blocks from readily available and stable
sulfonamides. The process is experimentally simple, mild, and high-yielding.
J. Raushel, S. M. Pitram, V. V. Fokin, Org. Lett.,
2008,
10, 3385-3388.