Preparation and thermal decomposition of N,N'-diacyl-N,N'-dialkoxyhydrazines: Synthetic applications and mechanistic insights

Article abstract of DOI:10.1021/ja00122a018

Oxidation of various O-alkyl hydroxamates 1 where R¹ was a keto-methoxime, benzoyl, aryl, or alkyl group with ceric ammonium nitrate (CAN) or nickel peroxide (NiO₂·H₂O) leads to the corresponding esters in high yield. This augurs well for the facile synthesis of highly hindered esters. Dimers of type 2 were identified as intermediates in these oxidations, and a combination of experimental and theoretical results suggest that these dimers decompose in a stepwise 1,1-elimination manner via intermediate nitrenes to furnish the esters and not via a stepwise 1,2-elimination sequence as previously thought.