New phosphorus amides as hydrogen bonding catalysts

合成并表征了新的磷酸酰胺和环二磷酰胺体系。这类磷酰胺的配合氢键给体不仅可用于氢键催化剂，还可用于阴离子受体。新型磷酰胺的模块化结构可以实现许多结构修饰，例如P=O， P=S或P= se单元，烷基或芳基连接到n原子以及不同的手性氨基醇或二氨基基。用紫外/可见滴定法测试不同离子对新型磷酰胺阴离子结合能力的影响。核磁共振和x射线分析以及量子化学计算将揭示离子是如何被新的氢键支架束缚的。为了与已建立的氢键催化剂进行比较，新磷酰胺的催化活性将首先在非立体选择反应中进行测试。新的手性磷酰胺将应用于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和关键的过渡结构。这些结果将用于设计更高效的基于磷酰胺的模块化氢键催化剂。

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.