Ambiphilic Phosphinines: a paradigm shift for aromatic phosphorus heterocycles?

两亲性膦膦：芳香族磷杂环的范式转变？

• 批准号: 416837419
• 负责人: Professor Dr. Christian Müller
• 金额: --
• 依托单位: Abteilung Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/416837419?language=en
• 关键词: Ambiphilic; Phosphinines; paradigm; shift; aromatic

In this continuation proposal, the very successful project on the chemistry of ambiphilic phosphinines is to be continued. Since the first successful synthesis of a phosphinine derivative by G. Märkl in 1966, the reactivity, coordination chemistry and application of these higher homologues of the pyridines have been determined by their electronic (and partly steric) properties: Phosphinines are characterised by an intrinsically weak nucleophilicity and basicity of the phosphorus atom, whereby its embedding in an aromatic system simultaneously gives rise to significant, electrophilic properties at the donor atom. This combination undoubtedly allows for interesting (follow-on) chemistry, but on the other hand also prohibits access to compounds typical for classical organophosphorus(III) compounds. In the course of the first funding phase, it became apparent that many of the originally postulated ideas and concepts for modifying the nucleophilic and electrophilic properties of phosphinines by introducing suitable substituents on the phosphorus heterocycle could be implemented very successfully. The diversity of the results promises a very multifaceted chemistry also in the second phase, whereby here, in addition to further research into the fundamental properties of functionalised phosphinines and access to still unknown diazaboryl-substituted phosphinines, applications in the field of (catalytic) bond activation reactions will be mainly targeted. The following goals are in focus: (i) diazaboryl-substituted phosphinines and their follow-up chemistry; (ii) insertion and cycloaddition reactions on phosphinine-borane/alane Lewis pairs; (iii) catalytic reactions with phosphinine-borane/alane Lewis pairs; (iv) bond activation reactions with electrophilic phosphinines; (v) reactions of electrophilic phosphinines with carbenes and fluorides. The previous results and preliminary work from the first funding period promise a successful implementation of the planned extensive studies also in the second project phase.

在这一持续提案中，将继续进行关于Ambiphilic磷化碱化学的非常成功的项目。自1966年首次通过G.Märkl成功合成磷酸衍生物以来，这些较高的吡啶的反应性，配位化学和这些较高的同源物的应用是由它们的电子（和部分空间）的特性确定的：磷酸碱的特征是在源自核能和基础上的重要性，从而使其具有较弱的核能和基础性，从而在其中构成了源容，从而构成了磷酸化的质量，从而呈现磷酸盐的质量，从供体原子的亲电性能。这种组合无疑可以进行有趣的（后续）化学反应，但另一方面也禁止进入经典有机磷（III）化合物的典型化合物。在第一个融资阶段的过程中，很明显，许多最初发布的思想和概念是通过在磷异源于磷异源上引入合适的亚物质来修改磷脂的核哲学和亲电性能。结果的多样性有望在第二阶段进行非常多方面的化学反应，除了进一步研究功能化的磷的基本特性，并获得了仍然未知的Diazaboryl取代的磷化素，其应用在（催化）键激活反应的领域中的应用也是针对的。以下目标是重点：（i）二氮杂二取代的磷酸及其随访化学； （ii）在磷酸 - 硼烷/Alane Lewis Pairs上的插入和环载反应； （iii）与磷酸 - 硼烷/Alane Lewis Pairs的催化反应； （iv）与亲电磷酸的键激活反应； （v）亲电磷酸与碳和氟化物的反应。先前的结果和初步资助期的初步工作有望在第二个项目阶段成功实施计划的广泛研究。