AI Article Synopsis
- The selective azidation-amination method uses sodium azide and copper(I) chloride to produce amine-azides from long-chain alkanoyl halobenzenes without additional additives.
- The reaction also involves an unexpected side reaction where alkyl groups are cleaved, likely through a radical mechanism, leading to the formation of alkyl nitriles.
- Mechanistic studies suggest that the process runs through intermediates known as 1-azido-4-alkanoyl benzenes, with the amination occurring under mild conditions and involving nitrenes.
Article Abstract
Selective azidation-amination of long-chain alkanoyl halobenzenes with sodium azide, promoted by copper(I) chloride, is reported. The protocol is, apart from CuCl and NaN, additive free and allows the isolation of versatile amine-azides. Alkyl cleavage occurs as a side reaction through an unusual Schmidt-type azide insertion adjacent to the carbonyl group, forming alkyl nitriles possibly via radical pathways. Mechanistic studies involving N labeling experiments and test substrates indicate that the reaction occurs via 1-azido-4-alkanoyl benzenes. The amination is applicable for substrates with electron-withdrawing groups and proceeds under mild conditions. The mechanism of the amine formation involves nitrenes. Intermediates were trapped by carrying out the reaction in the presence of the 2,2,6,6-(tetramethylpiperidin-1-yl)oxyl stable radical and characterized by high-resolution mass spectrometry. The intermediates are consistent with earlier mechanistic proposals.
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| http://dx.doi.org/10.1021/acs.joc.2c02549 | DOI Listing |
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