权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

New frustrated Lewis pair catalyzed addition reactions

新受挫路易斯对催化加成反应

基本信息

批准号：
258396946
负责人：
Professor Dr. Jan Paradies
金额：
--
依托单位：
Arbeitskreis Paradies
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2014
资助国家：
德国
起止时间：
2013-12-31 至 2017-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/258396946?language=en
关键词：
New frustrated Lewis pair catalyzed

项目摘要

The coexistence of a Lewis-acidic and a Lewis-basic site in solution, which leaves the individual reactivity unquenched, was introduced as the phenomenon of a frustrated Lewis pair (FLP). This feature led to the metal-free hydrogen cleavage and later to the activation of other small molecules, e. g. carbon dioxide, carbon monoxide or nitro oxides. The hydrogenation is the most appealing reaction in FLP-chemistry to date due to the high significance in chemistry. On the one hand, the biggest gain of FLP-chemistry is its complementarity to transition metal-based hydrogenations. A number of substrates e. g. halide- or diazonium-containing molecules are incompatible with transition metal-catalyzed hydrogenations. For those, FLP-chemistry can advance to a powerful and complementary method in process and research chemistry. On the other hand, novel FLP-mediated bond-activations (C-H or C-Si) must be found to advance this concept to a more general level. The presented research program targets both central issues of FLP-chemistry: (1) The FLP-catalyzed hydrogenation will be advanced to a powerful tool for the hydrogenation of transition-metal incompatible substrates, e. g. halide-bearing compounds, azo-derivatives or diazonium salts. These compound classes are currently reduced by stoichiometric reaction with borohydrides, hydrazine or sodium sulfite, giving rise to large amounts of waste material and safety hazards. Here, the FLP-catalyzed hydrogenation is the key technology to circumvent these issues. (2) The FLP-chemistry will be extended to transfer reactions of X-Y fragments, e. g. C-H, N-H and C-Si bonds, across multiple bonds. In analogy to the H-H transfer to olefins metal-free hydroaminations, hydrotrifluoromethylations and silylcyanations of unsaturated compounds will open new aspects of FLP-catalyzed reactions. The common overlap of both approaches is the simultaneous modulation of electronic and steric properties of the borane-derived Lewis-acids. Thereby the Lewis-acid's reactivity can be tuned to the application. These developments will not only broaden the FLP's reactivity but will also permit higher functional group tolerance. This will also lead to significant stability improvements of the borane towards air and moisture affording powerful methods for organic synthesis.

溶液中路易斯酸性和路易斯碱性位点的共存，使得个体反应性未淬灭，被引入作为受抑刘易斯对（FLP）现象。这一特征导致了无金属氢的裂解，后来又导致了其他小分子的活化。G.二氧化碳、一氧化碳或硝基氧化物。氢化反应是迄今为止FLP化学中最有吸引力的反应，因为它在化学上具有高度的重要性。一方面，FLP化学的最大收获是它对基于过渡金属的氢化的补充。一些基板e。G.含卤化物或重氮的分子与过渡金属催化的氢化不相容。对于这些，FLP化学可以发展成为过程和研究化学中强大的补充方法。另一方面，必须发现新的FLP介导的键活化（C-H或C-Si），以将这一概念提升到更普遍的水平。本研究计划主要针对FLP化学的两个核心问题：（1）FLP催化氢化将发展成为过渡金属不相容底物（如氢化物）的强有力工具; G.含卤素的化合物、偶氮衍生物或重氮盐。这些化合物类别目前通过与硼氢化物、肼或亚硫酸钠进行化学计量反应而减少，从而产生大量废料和安全危害。FLP催化加氢是解决这些问题的关键技术。(2)FLP化学将被扩展到X-Y片段的转移反应，例如。G. C-H、N-H和C-Si键，跨多个键。与烯烃的氢-氢转移类似，不饱和化合物的无金属氢胺化、氢三氟甲基化和甲硅烷基氰化将开辟FLP催化反应的新方面。这两种方法的共同重叠是硼烷衍生的路易斯酸的电子和空间位阻性质的同时调制。因此，路易斯酸的反应性可以根据应用进行调整。这些发展将不仅拓宽FLP的反应性，而且还将允许更高的官能团耐受性。这也将导致硼烷对空气和水分的稳定性显著改善，从而为有机合成提供有力的方法。