带有连接氰基的炔基杂芳族底物的分子内环化：一种合成稠合吡啶并杂环的策略。
Intramolecular Cyclization of Alkynylheteroaromatic Substrates Bearing a Tethered Cyano Group: A Strategy for Accessing Fused Pyridoheterocycles.
作者信息
Kraemer Niklas, Eason Erin M, Hoye Thomas R
机构信息
Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, United States.
出版信息
J Org Chem. 2023 Sep 1;88(17):12716-12726. doi: 10.1021/acs.joc.3c01411. Epub 2023 Aug 17.
Abstract
Heterocyclic substrates containing a conjugated alkyne and a pendant nitrile were shown to cyclize in an overall tetradehydro-Diels-Alder reaction to give products in which the initial heterocycle bears a newly fused pyridine ring. Base-promoted tautomerization of the alkyne to its isomeric allene allows this process to occur at ambient temperature. DFT studies support many of the mechanistic interpretations of the overall results.
摘要
含有共轭炔烃和侧腈基的杂环底物在总体上的四脱氢狄尔斯-阿尔德反应中发生环化，生成初始杂环带有新稠合吡啶环的产物。碱促进炔烃异构化为其异构体丙二烯，使得该过程能在室温下发生。密度泛函理论研究支持了对总体结果的许多机理解释。
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