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From masked carbenes to heterocycles: Novel potentially biological active difluoromethylene phosphonates as versatile building blocks

从掩蔽卡宾到杂环：新型潜在生物活性二氟亚甲基膦酸酯作为多功能结构单元

基本信息

批准号：
391415715
负责人：
Professor Dr. Gerd-Volker Röschenthaler
金额：
--
依托单位：
National Natural Science Foundation of China
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2018
资助国家：
德国
起止时间：
2017-12-31 至 2021-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/391415715?language=en
关键词：
masked carbenes heterocycles Novel potentially

项目摘要

This innovative project is aimed at elaborating methods to synthesize for the first time a variety of (2-diazo-1,1-difluoroethyl)phosphonates as valuable building blocks and their further application as reactive intermediates in the preparation of more complex molecules bearing at least one difluoromethylene phosphonate unit which could impart bioactivity onto the selected substrates. By varying the structure of the starting diazo compounds, their stability, reactivity and selectivity will be then verified. In some cases, asymmetric synthesis will be performed either via exploitation of enantiopure substrates or by addition of appropriate chiral catalysts. The following research tasks are planned, namely (1) the synthesis of (beta-diazo-alpha,alpha-difluoroethyl)phosphonates starting from the corresponding beta-ketophosphonates, (2) the synthesis of various fluorinated amino-, hydroxyl and thiohydroxyphosphonates via catalytic NH, SH and OH insertion reactions on carbenoid centres, (3) intermolecular cyclopropanation of selected alkenes and alkynes with (2-diazo-1,1-difluoroethyl)phosphonates, (4) intermolecular aromatic cycloadditions and substitutions, (5) ylide formation and subsequent cycloaddition or rearrangements reactions, (6) the synthesis of 5-membered heterocycles via [3+2] cycloaddition.

该创新项目旨在阐述首次合成各种（2-重氮基-1，1-二氟乙基）膦酸酯作为有价值的结构单元的方法，以及它们作为反应性中间体在制备更复杂的分子中的进一步应用，所述更复杂的分子具有至少一个二氟亚甲基膦酸酯单元，所述二氟亚甲基膦酸酯单元可以赋予所选底物生物活性。通过改变起始重氮化合物的结构，然后验证其稳定性、反应性和选择性。在某些情况下，不对称合成将通过利用对映体纯的底物或通过添加适当的手性催化剂来进行。本研究拟完成以下研究任务：（1）从相应的β-酮基膦酸酯开始，（2）通过在类卡宾中心上的催化NH、SH和OH插入反应，合成各种氟化的氨基-、羟基和硫代羟基膦酸酯，（3）用（2-重氮-1，1-二氟乙基）膦酸酯，（4）分子间芳香环加成和取代，（5）叶立德形成和随后的环加成或重排反应，（6）通过[3+2]环加成合成5-元杂环。