Radical Azidonation of Aldehydes
Lavinia Marinescu, Jacob Thinggaard, Ib B. Thomsen and Mikael Bols*
*Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000
Aarhus, Denmark, Email: bols
kemi.ku.dk
L. Marinescu, J. Thinggaard, I. B. Thomsen, M. Bols, J. Org. Chem., 2003, 68, 9453-9455.
DOI: 10.1021/jo035163v
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Abstract
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.
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proposed mechanism
Details
The document discusses a method for converting aliphatic and aromatic aldehydes to acyl azides using iodine azide (IN3) at 0-25 °C. At elevated temperatures, the acyl azides undergo Curtius rearrangement to form carbamoyl azides, which can be hydrolyzed to amines. This reaction follows a radical mechanism, where iodine radicals abstract hydrogen atoms from aldehydes, forming carbon-centered radicals that react with IN3 to produce acyl azides. The method is advantageous over traditional methods as it provides a direct route from aldehydes to amines, carbamates, or ureas, containing one carbon less. The reaction is performed in acetonitrile, and the yields of the products are high. The document also includes experimental procedures and safety warnings regarding the explosive nature of iodine azide. The study was supported by the European Commission, SNF, and the Lundbeck Foundation.
Safe radical azidonation using polystyrene supported diazidoiodate(I)
L. G. Marinescu, C. M. Pedersen, M. Bols, Tetrahedron, 2005, 61, 123-127.
Key Words
acyl azides, carbamoyl azides, urea derivatives, Curtius Rearrangement
ID: J42-Y2003-960
