School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Henan Key Laboratory of Organic Functional Molecule and Drug Innovation, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University , Xinxiang, Henan 453007, China.
J Org Chem. 2017 Oct 20;82(20):11230-11237. doi: 10.1021/acs.joc.7b01901. Epub 2017 Oct 9.
In this paper, a novel and efficient synthesis of 3-acylpyridines and pyridine-3-carboxylates through the oxidative one-pot sequential reactions of inactivated saturated ketones with electron-deficient enamines is presented. Mechanistically, the formation of the title compounds involves the in situ formation of an enone intermediate through an oxidative dehydrogenation of the saturated ketone substrate, followed by its [3+3] annulation with β-enaminone or β-enaminoester via a cascade process, including Michael addition, aldol type condensation, and oxidative aromatization.
本文提出了一种新颖高效的 3-酰基吡啶和吡啶-3-羧酸酯的合成方法，通过失电子烯胺与失活饱和酮的一锅氧化顺序反应实现。从机理上看，标题化合物的形成涉及通过饱和酮底物的氧化脱氢原位形成烯酮中间体，然后通过级联过程与β-烯胺酮或β-烯酰胺酯进行[3+3]环加成，包括迈克尔加成、醛醇缩合和氧化芳构化。
