去芳构化启动的三氟甲基芳香化合物的脱氟反应研究

批准号:
21961014
项目类别:
地区科学基金项目
资助金额:
40.0 万元
负责人:
刘晋彪
依托单位:
学科分类:
结构与反应机制
结题年份:
2023
批准年份:
2019
项目状态:
已结题
项目参与者:
刘晋彪
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中文摘要
由于氟原子的独特性能,含氟化合物在医药、农药及材料等领域备受关注。三氟甲基是一类常见的含氟基团,许多三氟甲基化合物也是大宗化工原料。但是C–F极高的键离解能,使得三氟甲基化合物的选择性脱氟及其转化在有机合成中极具吸引力和挑战性。近年来,去芳构化反应发展迅速,去芳构化策略已经成为构建复杂分子最直接有效的方法之一。值得关注的是,当三氟甲基苯的邻、对位含有质子供体时,其在碱性条件下也能发生去芳构化现象,脱除一分子HF,得到偕二氟取代的亚甲基醌(氮杂醌)中间体,进而发生系列转化反应。鉴于去芳构化策略的自身优势,拓展去芳构化启动的三氟甲基芳香化合物的脱氟及其转化反应是非常有价值的。为此,我们将系统研究去芳构化启动的三氟甲基芳香化合物的脱氟反应,尤其是苄位偕二氟的保留,同时拓展质子供体基团的种类;并且应用该策略构建一些具有潜在生物活性的含氟杂环化合物。
英文摘要
Over the past decades, fluorine-containing compounds have attracted much attention in the fields of pharmaceutic, pesticidal and material chemistry, in virtue of the unique properties of fluorine atoms. Particularly, trifluoromethyl is a well-known fluorine-containing group, and trifluoromethyl-containing compounds are available in the raw materials of many industrial chemicals. However, the dissociation of the C–F covalent bond in trifluoromethyl compounds requires high energy. Although the selective defluorination of trifluoromethyl compounds and their subsequent transformations are attractive strategies for C–F bond dissociation, these remain one of the most challenging topics in organic synthesis. To date, dearomatization strategies are straightforward and effective for the construction of those structurally-complicated compounds. When proton-donating groups are substituted on the ortho or para positions of trifluoromethyl benzene, dearomatization will occur in basic conditions, and then produce a gem-difluoromethylene quinone (aza-quinone) intermediate by eliminating a HF molecule, allowing a series of subsequent transformation reactions. Inspired by the promising advantages of dearomatization strategy, the expansion of defluorination and the conversion of trifluoromethylated aromatic compounds will be highly valuable in the field of synthetic chemistry. In this proposal, we aim to systematically study the dearomatization-initiated defluorination of trifluoromethylated aromatic compounds, especially the retention of difluorine in the benzyl group, as well as the expansion of various types of proton donating groups for dearomatization. We will also extensively investigate the present methodologies, with the aim to develop a series of fluorine-containing heterocyclic compounds with promising biological activity.
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DOI:10.1016/j.mcat.2022.112413
发表时间:2022-08
期刊:Molecular Catalysis
影响因子:4.6
作者:Miaofeng Ren;Xiaoyang Yan;Xiaojing Lai;Jinbiao Liu;Hongwei Zhou;Guanyinsheng Qiu
通讯作者:Miaofeng Ren;Xiaoyang Yan;Xiaojing Lai;Jinbiao Liu;Hongwei Zhou;Guanyinsheng Qiu
DOI:10.1039/d2ob01165d
发表时间:2022-07-29
期刊:ORGANIC & BIOMOLECULAR CHEMISTRY
影响因子:3.2
作者:Fang, Yu;Ren, Shangfeng;Yang, Min
通讯作者:Yang, Min
DOI:10.1016/j.tet.2022.133118
发表时间:2022
期刊:Tetrahedron
影响因子:--
作者:Rong-Fu Xu;Fu-Min Liao;Ying Cai;Jin-Biao Liu
通讯作者:Jin-Biao Liu
Ortho-Hydroxylative ipso-Cyclization of N-arylpropiolamide
N-芳基丙酰胺的邻位羟基化同位环化
DOI:10.1021/acs.joc.9b02590
发表时间:2020
期刊:Journal of Organic Chemistry
影响因子:3.6
作者:Wang Yu-Chao;Liu Jin-Biao;Zhou Hongwei;Xie Wenlin;Rojsitthisak Pornchai;Qiu Guanyinsheng
通讯作者:Qiu Guanyinsheng
DOI:--
发表时间:2020
期刊:有机化学
影响因子:--
作者:张磊;袁斯甜;王鹏;刘晋彪
通讯作者:刘晋彪
重氮介导的芳甲基骨架多官能团化反应研究
- 批准号:21762018
- 项目类别:地区科学基金项目
- 资助金额:38.0万元
- 批准年份:2017
- 负责人:刘晋彪
- 依托单位:
氧化脱羧启动的不饱和烃的选择性双官能团化反应研究
- 批准号:21502075
- 项目类别:青年科学基金项目
- 资助金额:21.0万元
- 批准年份:2015
- 负责人:刘晋彪
- 依托单位:
国内基金
海外基金
