
%0 Journal Article
%A Wille, Uta 
%A Andropof, Jilliarne 
%T <I>Corrigendum to</I>: Oxidation of Aromatic Alkynes with Nitrate Radicals (NO<sub>3</sub><sup>&#8226;</sup>): An Experimental and Computational Study on a Synthetically Highly Versatile Radical
%J Australian Journal of Chemistry
%D 2007/07/09
%V 60
%N 7
%P 547-547
%K 
%R https://doi.org/10.1071/CH07045_CO
%U https://www.publish.csiro.au/paper/CH07045_CO 
%X Addition of electro- and photochemically generated nitrate radicals, NO3&bull;, to the C&equiv;C triple bond of aromatic alkynes 9a&ndash;9h leads to formation of 1,2-diketones 10a&ndash;10h. Surprisingly, benzophenones 11a&ndash;11h 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&bull;. The key step to benzophenone formation is a &gamma;-cleavage at the stage of the vinyl radical with release of NO2&bull;, followed by Wolff rearrangement of the resulting &alpha;-oxo carbene. 
