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Paper | Special issue | Vol 95, No. 2, 2017, pp.994-1029
Published online, 21st February, 2017
DOI: 10.3987/COM-16-S(S)70
Alpha-Oxidation of Amine Derivatives by bis(2,2,2-Trichloroethyl) Azodicarboxylate and Application of Its Products as Iminium Ion Equivalents

Shinobu Honzawa,* Mitsuaki Uchida, Takuya Tashiro, and Takumichi Sugihara*

*Faculty of Pharmaceutical Sciences, Niigata University of Pharmacy and Applied Life Sciences (NUPALS), Niigata 956-8603, Japan

Abstract

Alpha-oxidation of amine derivatives by azodicarboxylate was examined. Among several azodicarboxylate esters and amides tested, bis(2,2,2-trichloroethyl) azodicarboxylate, that has highly electrophilic 2,2,2-trichloroethoxycarbonyl functional groups, was found to have excellent oxidation reactivity. Acylated or carbamoylated amines were suitable substrates for this reaction condition. Tertially amines could react in the same manner, but spontaneous elimination of hydrazinyl group occurred to give dimerized products. The reaction products were found to react with nucleophiles in the presence of Lewis or Brønsted acid catalyst. This strongly suggests that the reaction products, alpha-hydrazinated amine derivatives, might serve as carbonyl group equivalents, very useful intermediates in synthetic organic chemistry.