PREPARATION AND THERMAL-DECOMPOSITION OF N,N'-DIACYL-N,N'-DIALKOXYHYDRAZINES - SYNTHETIC APPLICATIONS AND MECHANISTIC INSIGHTS
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Oxidation of various O-alkyl hydroxamates 1 where R1was a keto-methoxime, benzoyl, aryl, or alkyl group with ceric ammonium nitrate (CAN) or nickel peroxide (NiO2H2O) 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. 1995, American Chemical Society. All rights reserved.