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The development of selective catalysts for novel C-N- and C-C-bond forming reactions - a contribution to a more sustainable chemistry

开发用于新型 C-N- 和 C-C- 键形成反应的选择性催化剂 - 对更可持续化学的贡献

基本信息

批准号：
221509923
负责人：
Professor Dr. Rhett Kempe
金额：
--
依托单位：
Arbeitsgruppe Anorganische Chemie II
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2012
资助国家：
德国
起止时间：
2011-12-31 至 2018-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/221509923?language=en
关键词：
development selective catalysts novel bond

项目摘要

Aims of the submitted proposal are the development of novel catalytic reactions and the development of catalyst classes able to mediate these reactions efficiently. Dehydrogenation and condensation steps are combined in the reactions to synthesize N aromatic compounds from various alcohol components. Alcohols are accessible via pyrolysis from lignocellulose, a natural resource available in large amounts and barely used. Thus, the catalytic concepts developed in the proposal can be understood as a contribution to a more sustainable chemistry.The state of the art in the field of ADC (acceptorless dehydrogenative condensations) for the catalytic synthesis of N aromatic compounds is internationally strongly influenced by our contributions. In the last (first) period of funding, we published five manuscripts, partially in high impact journals like Nature Chemistry and Angewandte Chemie. The investigation of the following interlinked sub-projects is proposed for the second period of funding.Development of novel catalytic reactionsFirstly, the extension of the ADC concept towards the catalytic synthesis of N-rich aromatics is proposed. In this sub-project, we plan, on the one hand side, to investigate reactions of amino alcohols with various C-N multiply bonded species. Furthermore, we plan the development of multi component reactions, in which up to three alcohol components, ammonia and nitriles are linked to highly functionalized pyrimidines. Conceptually new is the third aim. ADC is combined with hydrogenation and dehydrogenation steps to allow a broadly applicable and sustainable access to polycyclic N aromatic compounds.Catalyst designThree aims are in focus with regard to the catalyst design part of the proposal. Firstly, we plan the development of novel Ir and Ru complex-catalysts stabilized by hydrolysis stable ligands. Water is eliminated in ADC reactions and more stable catalysts are imaginable if the used ligands tolerate it. Preliminary work shows a superiority of such catalyst in comparison to the Ir complex-catalysts used in the pyrrole synthesis so far. Secondly, we are interested in developing Co and Fe catalysts for ADC. The use of inexpensive base metals as an alternative for the so far used Ir and Ru catalysts seems possible as preliminary work with Co indicates. Thirdly, the development of efficient reusable catalysts for the selective hydrogenation of arenes and the dehydrogenation of cycloalkanes is proposed. They are needed for the synthesis of polycyclic N aromatic compounds via a hydrogenation, ADC and dehydrogenation sequence.

提交的提案的目的是开发新的催化反应和开发能够有效地调解这些反应的催化剂类别。在反应中结合脱氢和缩合步骤，从各种醇组分合成N个芳香族化合物。酒精可以通过热解木质纤维素来获得，木质纤维素是一种大量可用但几乎没有使用的自然资源。因此，建议中开发的催化概念可以被理解为对更可持续的化学的贡献。我们的贡献在国际上对催化合成N芳香族化合物的ADC(无接受脱氢缩合)领域的技术水平有很大的影响。在最后(第一)资助期间，我们发表了五篇手稿，部分发表在《自然化学》和《Angewandte Chemie》等影响较大的期刊上。在第二阶段的资助中，我们建议进行以下相互关联的子项目的研究。新型催化反应的开发首先，建议将ADC的概念扩展到富N芳烃的催化合成中。在这个子项目中，我们计划一方面研究氨基醇与各种C-N多键物种的反应。此外，我们还计划开发多组分反应，在该反应中，多达三种醇组分，氨和腈与高度官能化的嘧啶相连。概念上的新是第三个目标。ADC与加氢和脱氢步骤相结合，允许广泛适用和可持续地获得多环N芳烃化合物。催化剂设计关于提案中的催化剂设计部分，有三个目标是重点。首先，我们计划开发由稳定的水解配体稳定的新型Ir和Ru络合催化剂。水在ADC反应中被消除，如果被使用的配体容忍水，则可以想象更稳定的催化剂。初步研究表明，与目前吡咯合成中使用的Ir络合物催化剂相比，该催化剂具有一定的优越性。其次，我们有兴趣开发用于ADC的Co和Fe催化剂。钴的初步工作表明，使用廉价的贱金属作为迄今使用的Ir和Ru催化剂的替代品似乎是可能的。第三，提出了开发高效可重复使用的芳烃选择加氢和环烷烃脱氢催化剂的建议。它们是通过加氢、ADC和脱氢序列合成多环N-芳香族化合物所需的。