Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University , Xinxiang, Henan 453007, P. R. China.
J Org Chem. 2017 Jun 16;82(12):6125-6132. doi: 10.1021/acs.joc.7b00686. Epub 2017 May 24.
A novel in situ generated TEMPO oxoammonium salt mediated one-pot tandem reaction has been developed for the straightforward construction of pyrrolin-4-ones from readily available β-oxoamides with amine hydrochlorides. The reaction tolerates various functional groups and represents a reliable method for the synthesis of highly substituted pyrrolin-4-ones in good yields under mild conditions. Detailed mechanistic studies disclosed that TEMPO oxoammonium salt generated in situ was crucial for the transformation involving the formation of enaminone precursors in situ by condensation of the β-oxoamides with amines, followed by sequential oxidative coupling with β-oxoamides, intramolecular cyclization, and 1,2-alkyl migration steps.
一种新型的 TEMPO 氧铵盐介导的一锅串联反应已经被开发出来，用于从易得的β-氧代酰胺和胺盐酸盐中直接构建吡咯啉-4-酮。该反应可以容忍各种官能团，代表了一种在温和条件下以良好收率合成高取代吡咯啉-4-酮的可靠方法。详细的机理研究表明，原位生成的 TEMPO 氧铵盐对于转化过程至关重要，该转化过程涉及β-氧代酰胺与胺缩合原位形成烯胺酮前体，然后与β-氧代酰胺进行连续氧化偶联、分子内环化和 1,2-烷基迁移步骤。
