New phosphorus amides as hydrogen bonding catalysts

作为氢键催化剂的新型磷酰胺

• 批准号: 317115582
• 负责人: Professor Dr. Bernd Goldfuß
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/317115582?language=en
• 关键词: New; phosphorus; amides; hydrogen; bonding

New phosphorus acid amide and cyclodiphosphazane systems will be synthesized and characterized.The cooperative hydrogen bonding donors of such phosphorus amides will be applied in anion receptors as well as in hydrogen bonding catalysts.The modular constructions of the new phosphorus amides enable many structural modifications, e.g. of P=O, P=S or P=Se-units, of alkyl or aryl groups attached to N-atoms as well as with different chiral amino alcoholic- or diamino- groups.The ability for anion binding will be tested for the new phosphorus amides with different ions using UV/Vis titrations. NMR- and X-ray-analyses as well as quantum chemical computations will reveal how ions are bound by the new hydrogen bonding scaffolds.For a comparison with established hydrogen bonding catalysts, the catalytic activity of the new phosphorus amides will first be tested in non-stereoselective reactions. The new, chiral phosphorus amides will then be applied in enantioselective catalytic couplings of C-C- and C-heteroatoms. Supported by X-ray analyses, NMR-experiments and quantum chemical computations, the favored binding modes of substrates and reagents and the crucial transition structures will be studied. These results will then be employed for the design of even more efficient modular hydrogen bonding catalysts based on phosphorus amides.

本论文将合成和表征新的磷酰胺和环二磷氮烷体系，这类磷酰胺的协同氢键给体将被应用于阴离子受体和氢键催化剂中，新的磷酰胺的模块化结构使许多结构修饰成为可能，例如P=O，P=S或P= Se-单元，用UV/维斯滴定法测试了新的磷酰胺与不同离子的阴离子结合能力。核磁共振和X射线分析以及量子化学计算将揭示离子如何被新的氢键骨架结合。为了与现有的氢键催化剂进行比较，新的磷酰胺的催化活性将首先在非立体选择性反应中进行测试。新的手性磷酰胺将被应用于C-C-和C-杂原子的对映选择性催化偶联。在X射线分析、核磁共振实验和量子化学计算的支持下，将研究底物和试剂的有利结合模式以及关键的过渡结构。这些结果将用于设计更有效的基于磷酰胺的模块化氢键催化剂。

项目成果

Hydrogen-bonding cyclodiphosphazanes: superior effects of 3,5-(CF3)2-substitution in anion-recognition and counter-ion catalysis

• DOI: 10.1039/c7nj04660j
• 发表时间: 2018-03
• 期刊: New Journal of Chemistry
• 影响因子: 3.3
• 作者: F. Wolf;J. Neudörfl;B. Goldfuss