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

作为合成结构单元的对氨基和烷氧基取代的磷酯衍生物

• 批准号: 426729495
• 负责人: Professor Dr. Dietrich Gudat
• 金额: --
• 依托单位: Institut für Anorganische Chemie (IAC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2019
• 资助国家: 德国
• 起止时间: 2018-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/426729495?language=en
• 关键词: Derivatives; Amino; Alkoxy; substituted; Phosphanides

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.

亲核碱金属膦化物R1 R2 PM或其硼烷配合物与亲电试剂的偶联反应是磷原子引入分子骨架的基本方法之一，在有机（元素）化学、催化、配位化学等领域被广泛用于膦衍生物的合成。在这个项目中，以前未知的磷酰胺衍生物将产生，其磷原子携带吸电子氨基和烷氧基取代基。这种类型的物种是感兴趣的合成积木，因为使用亲核试剂的可能性，以转移亲电子特性的磷原子亲电子基板。这种反应模式也可以被理解的意义上的极性反转的转移膦基片段，并开辟了一个合成策略，这是互补的使用磷酰胺作为来源的亲核膦基部分，并可以预期有一个巨大的潜力，组装膦与取代模式，迄今难以或不可能实现。该项目的具体重点是阐述金属-二氨基-和二烷氧基膦化物的硼烷加合物的合理合成，它们的综合表征，以及它们的化学反应性的彻底评价。在这个过程中，合成二氨基-/二烷氧基膦与一个额外的正电取代基的工作，和他们的化学，这已被广泛忽视到目前为止，是要开发。作为一项特殊的挑战，将继续研究在筹备工作中获得的证据，根据这些证据，金属化二氨基膦也可能适合作为转移磷（I）碎片的“次膦源”。