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无金属条件下通过腈基活化和[2+2+2]环加成反应构建多取代嘧啶

Metal Free Access to Polysubstituted Pyrimidines via Nitrile Activation and [2+2+2] Cycloaddition.

机构信息

Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, P. R. China.

Henan University of Animal Husbandry and Economy, Zhengzhou, 450001, P. R. China.

出版信息

Chemistry. 2021 Dec 15;27(70):17565-17569. doi: 10.1002/chem.202103219. Epub 2021 Oct 22.

DOI:10.1002/chem.202103219
PMID:34626013
Abstract

Tf O mediated intermolecular / intramolecular [2+2+2] cycloaddition between alkynes and nitriles has been developed for efficient construction of polysubstituted pyrimidines and bicyclopyrimidines. In presence of Tf O, aza-allene species were generated in situ through nitrile activation and subsequently participated in the [2+2+2] cycloaddition, which was fully supported by deuteration experiments. The reaction had good substrate extensibility with moderate to excellent yield including trimethylsilylalkynes. The method was utilized as a synthetic tool in the preparation of a luminescent metal complex.

摘要

TfO 介导的炔烃和腈之间的分子间/分子内 [2+2+2]环加成已被开发用于高效构建多取代嘧啶和双环嘧啶。在 TfO 的存在下,通过腈的活化原位生成氮杂丙二烯物种,随后参与 [2+2+2]环加成,这完全得到氘代实验的支持。该反应具有良好的底物扩展性,包括三甲基硅基炔烃,产率中等至优秀。该方法被用作合成工具,用于制备发光金属配合物。

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