An atom-economic thermal α,β-difunctionalization of various styrenes with readily prepared azodioxy compounds is reported. Mechanistic studies reveal that the starting azodioxy compounds can thermally be cleaved to the corresponding C-nitroso compounds, which under these thermal conditions further homolyze to generate reactive C-radicals along with the persistent NO radical. In the presence of a styrene, C-radical addition with subsequent nitrosylation followed by tautomerization is occurring, resulting in an overall styrene β-alkylation-α-oximation reaction.
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