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.

提交的建议的目的是发展新型催化反应以及能够有效介导这些反应的催化剂类别的发展。在合成各种酒精成分的N芳族化合物的反应中合并了脱氢和冷凝步骤。可以通过木质纤维素的热解获得醇，这是一种自然资源，可提供大量的自然资源，几乎没有使用。因此，该提案中开发的催化概念可以理解为对更可持续的化学的贡献。对于n芳族化合物的催化综合，ADC领域的最新状态（无受体脱氢凝结）在国际上受到我们的强烈影响，受我们的影响。贡献。在最后（第一个）资金时期，我们发表了五本手稿，部分在自然化学和Angewandte Chemie等高影响期刊上。在第二阶段的资金阶段提出了以下相互联系的子项目的研究。新型催化反应的开发首先提出了ADC概念向富含N-氧化N的催化合成的扩展。在此子项目中，我们一方面计划研究氨基醇与各种C-N倍数键合的反应。此外，我们计划了多组分反应的发展，其中最多三种酒精成分，氨和硝酸盐与高度功能化的嘧啶有关。从概念上讲，新的是第三个目标。 ADC与氢化和脱氢步骤结合使用，允许广泛适用且可持续地使用多环状N芳族化合物。Catalyst DesignThree Aims的重点是该提案的催化剂设计部分。首先，我们计划通过水解稳定配体稳定的新型IR和RU复合催化剂的开发。在ADC反应中消除了水，如果用过的配体耐受性耐受性，则可以想象到更稳定的催化剂。与迄今为止吡咯合成中使用的IR复合物催化剂相比，初步工作表明了这种催化剂的优势。其次，我们对为ADC开发CO和FE催化剂感兴趣。将廉价的碱金属用作迄今为止使用的IR和RU催化剂的替代方法似乎是可以使用CO的初步工作。第三，提出了有效可重复使用的催化剂的发展，以选择性氢化和环烷烃的脱氢作用。它们是通过氢化，ADC和脱氢序列合成多环状N芳族化合物所需的。