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铜（II）-双氧促进的硝基甲烷活化：用于合成取代的2-羟基亚氨基-2-苯基乙腈和邻苯二甲酰亚胺的氮供体

Copper(II)-Dioxygen Facilitated Activation of Nitromethane: Nitrogen Donors for the Synthesis of Substituted 2-Hydroxyimino-2-phenylacetonitriles and Phthalimides.

作者信息

Xiang Shiqun, Li Yinghua, Fan Weibin, Jin Jiang, Zhang Wei, Huang Deguang

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, China.

School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, China.

出版信息

Front Chem. 2021 Jan 29;8:622867. doi: 10.3389/fchem.2020.622867. eCollection 2020.

DOI:10.3389/fchem.2020.622867
PMID:33585402
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7878530/
Abstract

A simple and efficient method is explored for the synthesis of 2-hydroxyimino-2-phenylacetonitriles (2) and phthalimides (4), by using nitromethane as nitrogen donors. Both reactions are promoted by Cu(II) system with the participation of dioxygen as an oxidant. The scope of the method has been successfully demonstrated with a total of 51 examples. The flexible and diversified characteristics of reactions are introduced in terms of electronic effect, steric effect, position of substituted groups, and intramolecular charge transfer. Experimental studies suggest that the methyl nitrite could be a precursor in the path to the final products. A possible reaction mechanism is proposed, including the Cu(II)/O-facilitated transformation of nitromethane to methyl nitrite, the base-induced formation of 2-hydroxyimino-2-phenylacetonitriles, and the base-dioxygen-promoted formation of phthalimides.

摘要

探索了一种简单高效的方法，以硝基甲烷作为氮供体来合成2-羟基亚氨基-2-苯基乙腈（2）和邻苯二甲酰亚胺（4）。这两个反应均由Cu（II）体系促进，并有氧气作为氧化剂参与。该方法的适用范围已通过总共51个实例成功得到证明。从电子效应、空间效应、取代基位置和分子内电荷转移方面介绍了反应的灵活多样的特点。实验研究表明，亚硝酸甲酯可能是通往最终产物途径中的前体。提出了一种可能的反应机理，包括Cu（II）/O促进的硝基甲烷向亚硝酸甲酯的转化、碱诱导的2-羟基亚氨基-2-苯基乙腈的形成以及碱-氧气促进的邻苯二甲酰亚胺的形成。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/5ae8b636813a/fchem-08-622867-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/dc6627e5f65e/fchem-08-622867-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/4840e91fa8b8/fchem-08-622867-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/895c459dd9a7/fchem-08-622867-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/782208e6b869/fchem-08-622867-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/3e4fae0df19b/fchem-08-622867-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/5ae8b636813a/fchem-08-622867-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/dc6627e5f65e/fchem-08-622867-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/4840e91fa8b8/fchem-08-622867-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/895c459dd9a7/fchem-08-622867-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/782208e6b869/fchem-08-622867-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/3e4fae0df19b/fchem-08-622867-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8c47/7878530/5ae8b636813a/fchem-08-622867-g006.jpg

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本文引用的文献

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