作为一种荧光偶联反应的吡啶叶立德-炔环加成反应的研究。
Investigation of the Pyridinium Ylide--Alkyne Cycloaddition as a Fluorogenic Coupling Reaction.
作者信息
Bonte Simon, Ghinea Ioana Otilia, Dinica Rodica, Baussanne Isabelle, Demeunynck Martine
机构信息
Department of Pharmacochemistry, Université Grenoble Alpes, CNRS, DPM UMR 5063, F-38041 Grenoble, France.
Department of Chemistry, Physics and Environment, Faculty of Science and Environment, "Dunarea de Jos" University of Galati, 111 Domneasca Street, 800201 Galati, Romania.
出版信息
Molecules. 2016 Mar 10;21(3):332. doi: 10.3390/molecules21030332.
The cycloaddition of pyridinium ylides with alkynes was investigated under mild conditions. A series of 13 pyridinium salts was prepared by alkylation of 4-substituted pyridines. Their reactivity with propiolic ester or amide in various reaction conditions (different temperatures, solvents, added bases) was studied, and 11 indolizines, with three points of structural variation, were, thus, isolated and characterized. The highest yields were obtained when electron-withdrawing groups were present on both the pyridinium ylide, generated in situ from the corresponding pyridinium salt, and the alkyne (X, Z = ester, amide, CN, carbonyl, etc.). Electron-withdrawing substituents, lowering the acid dissociation constant (pKa) of the pyridinium salts, allow the cycloaddition to proceed at pH 7.5 in aqueous buffers at room temperature.
在温和条件下研究了吡啶叶立德与炔烃的环加成反应。通过4-取代吡啶的烷基化制备了一系列13种吡啶盐。研究了它们在各种反应条件（不同温度、溶剂、添加碱）下与炔丙酸酯或酰胺的反应活性，从而分离并表征了11种具有三种结构变异点的中氮茚。当由相应吡啶盐原位生成的吡啶叶立德和炔烃上都存在吸电子基团（X、Z = 酯、酰胺、腈、羰基等）时，可获得最高产率。吸电子取代基降低了吡啶盐的酸解离常数（pKa），使得环加成反应能够在室温下于pH 7.5的水性缓冲液中进行。
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