Oxidation of Aromatic Alkynes with Nitrate Radicals (NO3•): An Experimental and Computational Study on a Synthetically Highly Versatile Radical
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Addition of electro- and photochemically generated nitrate radicals, NO3•, to the C≡C triple bond of aromatic alkynes 9a–9h leads to formation of 1,2-diketones 10a–10h. Surprisingly, benzophenones 11a–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•. 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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2015 ◽
Vol 1096
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pp. 407-412
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2021 ◽
2005 ◽
Vol 109
(46)
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pp. 21471-21475
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