Autoxidation of Heterocyclic Aminals

The autoxidation reactions of 2-acyl-2,3-dihydroquinazolin-4(1 H )-ones 4a and 5a and 2,2'-bis(dihydroquinazolinone) 6a are described. These reactions generate aminyl radicals that undergo β-C-C cleavage, and subsequent reactions of the resulting C-based radicals with O 2 lead to diverse products with good selectivity, depending on the structure of the substrate. Oxidation of 4a , in which the 2-acyl group is part of a cyclic acenaphthenone unit, yields a heterocyclic C -hydroperoxylaminal via 1,2-acyl migration. Oxidation of 5a , which contains a 2-acetyl group, yields peracetic acid and a quinazolinone product. Oxidation of 6a forms a bis(quinazolinone) by net dehydrogenation.