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Updated: Aug 13, 2025

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Copper(I) Chloride Mediated Amination of Halobenzenes via Azides: Scope, Mechanistic Aspects, and C-C Cleavage
Max Roemer1, Nicholas Proschogo1, Ian Luck2
1School of Chemistry, The University of Sydney, Sydney, New South Wales 2006, Australia.
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 NaN3, 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 15N 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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