Dispersion Effects on Reactivity and Chemo-, Regio- and Stereoselectivity in Organocatalysed Domino Reactions: A Joint Experimental and Theoretical Study

有机催化多米诺反应中反应性以及化学、区域和立体选择性的分散效应：联合实验和理论研究

• 批准号: 271358765
• 负责人: Professor Dr. Andreas Görling
• 金额: --
• 依托单位: Lehrstuhl für Theoretische Chemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/271358765?language=en
• 关键词: Dispersion; Effects; Reactivity; Chemo; Regio

This joint experimental and theoretical project aims at the development of facile and environmentally friendly organocatalytic multi-step domino reactions exploiting dispersion interactions in these novel systems. We plan to conduct a series of multi-component domino reactions involving readily available nitroolefins and aldehydes, as well as CH-acidic malononitrile already known for its broad application and its versatile use as an exceptionally reactive compound. We will mainly focus on the following three unprecedented reactions: (i) three-component two-step domino Knoevenagel/vinylogous Michael reaction; (ii) three-component five-step branched domino Knoevenagel/nitro-Michael/nitroalkane-Michael/intramolecular condensation/isomerization; (iii) two-component six-step domino Knoevenagel/dimerisation/ intermolecular condensation/intramolecular aza-Michael/intramolecular condensation/ isomerization reaction. Detailed mechanistic investigations will be performed using conventional density-functional methods in conjunction with semiempirical van der Waals corrections as well as novel highly accurate density-functional methods to shed light on the intriguing differences in chemoselectivity, regioselectivity and stereoselectivity in these organocatalysed domino transformations, and, in particular, to understand and exploit the influence of dispersion interaction in these transformations. Taking the envisioned domino reactions as test cases, computational setups for a density-functional based description of organocatalysis will be developed.

这个联合实验和理论项目的目的是在这些新的系统中利用分散相互作用的简易和环境友好的有机催化多步多米诺反应的发展。我们计划进行一系列的多组分多米诺反应，涉及容易获得的硝基烯烃和醛，以及CH-酸性丙二腈已经知道其广泛的应用和其作为一个非常活跃的化合物的多用途。我们将主要关注以下三个前所未有的反应：（i）三组分两步多米诺Knoevenagel/乙烯基Michael反应;（ii）三组分五步支化多米诺Knoevenagel/硝基Michael/硝基烷烃Michael/分子内缩合/异构化反应;（iii）两组分六步多米诺Knoevenagel/二聚/分子间缩合/分子内氮杂Michael/分子内缩合/异构化反应。详细的机理研究将使用传统的密度泛函方法结合半经验的货车德瓦尔斯修正以及新的高度准确的密度泛函方法来阐明有趣的化学选择性，区域选择性和立体选择性在这些有机催化的多米诺骨牌转换的差异，特别是要了解和利用这些转换中的分散相互作用的影响。以设想的多米诺骨牌反应作为测试用例，计算设置为密度泛函为基础的描述有机催化。