Design and synthesis of very strong pi-acceptor ancillary ligands. Applications in Au(I) and Pt(II) catalysis and the synthesis of natural products

设计和合成非常强的π受体辅助配体。

• 批准号: 234417750
• 负责人: Professor Dr. Manuel Alcarazo
• 金额: --
• 依托单位: Institut für Organische und Biomolekulare Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/234417750?language=en
• 关键词: Design; synthesis; very; strong; pi

pi-acid catalysis, employing mainly Au(I) and Pt(II) based catalysts, has emerged in the last decade as one of the most efficient tools for the promotion of rearrangements in unsaturated organic substrates providing thus an exquisite entry for the synthesis of intricate skeletons that may be otherwise difficult to prepare. Herein, the employment of new ancillary ligands with enhanced pi-acceptor character is proposed as a strategy to improve the reactivity and broaden the substrate scope of some of these Au- or Pt-derived catalysts. Based in our previous findings, polycationic phosphines and also rigid phosphino-borane chelating architectures are the ligands of choice for this task. Thus, syntheses for all the new ligands as well as model reactions to ascertain their role are proposed. Finally, possible applications in the field of natural product synthesis are described.

主要使用基于Au（I）和Pt（II）的催化剂的π-酸催化在过去十年中已经作为促进不饱和有机底物中重排的最有效工具之一出现，从而为合成可能难以制备的复杂骨架提供了一个极好的入口。在本文中，提出采用具有增强的π-受体特性的新辅助配体作为改善这些Au-或Pt-衍生催化剂中的一些的反应性和拓宽底物范围的策略。根据我们之前的发现，聚阳离子膦和刚性膦基硼烷螯合结构是这项任务的首选配体。因此，合成所有新的配体以及模型反应，以确定其作用的建议。最后，在天然产物合成领域的可能应用进行了描述。

项目成果

Bis- and tris(pyrazolyl)borate/methane-stabilized P(III) -centered cations.

双和三(吡唑基)硼酸盐/甲烷稳定的 P(III) 中心阳离子

• DOI: 10.1002/chem.201402636
• 发表时间: 2014
• 期刊: Chemistry
• 作者: G. Gopakumar;P. Gualco;W. Thiel;M Alcarazo
• 通讯作者: M Alcarazo

Bis(cyclopropenium)phosphines: Synthesis, Reactivity, and Applications.

双(环丙烯)膦：合成、反应性和应用

• DOI: 10.1002/chem.201601759
• 发表时间: 2016
• 期刊: Chemistry
• 作者: G. Mehler;P. Linowski;J. Carreras;A. Zanardi;J. W. Dube;M. Alcarazo
• 通讯作者: M. Alcarazo

Synthese, Struktur und Anwendungen von Pyridiniumphosphanen

• DOI: 10.1002/ange.201401073
• 发表时间: 2014-08
• 期刊: Angewandte Chemie
• 作者: Hendrik Tinnermann;C. Wille;Manuel Alcarazo