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Article << Previous     |     Next >>   Contents Vol 60(6)

Oxidation of Aromatic Alkynes with Nitrate Radicals (NO3): An Experimental and Computational Study on a Synthetically Highly Versatile Radical

Uta Wille A B C, Jilliarne Andropof A B

A School of Chemistry, University of Melbourne, Melbourne VIC 3010, Australia.
B Bio21 Molecular Science and Biotechnology Institute, 30 Flemington Road, Melbourne VIC 3010, Australia.
C Corresponding author. Email: uwille@unimelb.edu.au
 
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Abstract

Addition of electro- and photochemically generated nitrate radicals, NO3, to the C≡C triple bond of aromatic alkynes 9a9h leads to formation of 1,2-diketones 10a10h. Surprisingly, benzophenones 11a11h are obtained as by-products, which formally result from loss of a carbon atom. Density functional studies performed with the BHandHLYP method in combination with various basis sets revealed that 1,2-diketones result from 5-endo cyclization of the initially formed vinyl radical and loss of NO. The key step to benzophenone formation is a γ-cleavage at the stage of the vinyl radical with release of NO2, followed by Wolff rearrangement of the resulting α-oxo carbene.

   
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