Derivatives of P-Amino- and Alkoxy-substituted Phosphanides as Synthetic Building Blocks

亲核碱金属磷酸盐R1R2PM或它们的硼烷配合物与亲电试剂偶联是磷原子进入分子骨架的基本方法之一，已被用于元素有机化学、催化或配位化学中的许多膦烷衍生物的合成。在这个项目中，将生产出以前未知的磷酰胺衍生物，其磷原子携带有吸电子的氨基和烷氧基取代基。由于使用亲核试剂将具有亲电性质的磷原子转移到亲电的底物上的可能性，这种类型的物种作为合成构建块是有兴趣的。这种反应模式也可以从转移的磷酰基片段的极性反转的意义上理解，并开辟了一种合成策略，这是对磷酰胺作为亲核磷酰基部分来源的既定用途的补充，并有望在组装具有迄今为止难以或不可能实现的取代模式的膦方面具有巨大的潜力。该项目的具体重点是阐述确定的金属二氨基和二烷氧基膦的硼烷加合物的合理合成，它们的全面表征，以及对它们的化学反应活性的彻底评价。在这一过程中，将合成具有额外正电取代基的二氨基/二烷氧基膦，并发展其被广泛忽视的化学。作为一项特别的挑战，将寻求在筹备工作期间获得的证据，根据这些证据，金属二氨基膦也可作为转移磷(I)碎片的“亚膦来源”。

The coupling of nucleophilic alkali metal phosphanides R1R2PM or their borane complexes with electrophiles is one of the basic methods for incorporation of phosphorus atoms into molecular frame-works and has been used in many syntheses of phosphane derivatives in (element)organic chemistry, catalysis, or coordination chemistry. In this project, previously unknown phosphanide derivatives will be produced, whose phosphorus atoms carry electron withdrawing amino and alkoxy substituents. Species of this type are of interest as synthetic building blocks because of the possibility of using a nucleophilic reagent to transfer a phosphorus atom of electrophilic character to an electrophilic substrate. This reaction pattern can also be understood in the sense of a polarity reversal of the transferred phosphanyl fragment and opens up a synthetic strategy, which is complementary to the established use of phosphanides as a source of nucleophilic phosphanyl moieties and can be expected to have a great potential for the assembly of phosphines with substitution patterns that were hitherto difficult or impossible to realize. Concrete focus of the project is the elaboration of rational syntheses for defined borane adducts of metal-diamino- and dialkoxyphosphanides, their comprehensive characterization, and the thorough evaluation of their chemical reactivity. In the process, syntheses for diamino-/dialkoxy phosphines with an additional electropositive substituent are to be worked out, and their chemistry, which has been widely neglected so far, is to be developed. As a particular challenge, evidence obtained during preparatory work will be pursued, according to which metallated diamino-phosphanes could also be suitable as a "phosphinidene source" for the transfer of phosphorus (I) fragments.