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

提交的提案的目的是开发新型催化反应和开发能够有效介导这些反应的催化剂类别。在反应中将脱氢和缩合步骤组合以从各种醇组分合成N芳族化合物。醇类可通过热解从木质纤维素获得，木质纤维素是一种大量可用且几乎不使用的自然资源。因此，在该提案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。ADC（无受体缩合）领域的最新技术在国际上受到我们的贡献的强烈影响。在上一个（第一个）资助期内，我们发表了五篇论文，部分发表在高影响力的期刊上，如《自然化学》和《应用化学》。第二个资助期内，建议对以下相互关联的子项目进行研究：新型催化反应的开发首先，建议将ADC概念扩展到富氮芳烃的催化合成。在这个子计划中，我们一方面计划研究氨基醇与各种C-N多键物种的反应。此外，我们计划开发多组分反应，其中多达三种醇组分，氨和腈与高度官能化的嘧啶连接。第三个目标是新概念。ADC与加氢和脱氢步骤相结合，可以广泛应用和可持续地获得多环N芳族化合物。催化剂设计催化剂设计部分的重点是三个目标。首先，我们计划开发新型的Ir和Ru络合物催化剂，由水解稳定的配体稳定。水被消除在ADC反应和更稳定的催化剂是可以想象的，如果所使用的配体容忍it. Preliminary工作表明，这种催化剂的优越性相比，在吡咯合成中使用的Ir配合物催化剂迄今。其次，我们有兴趣开发用于ADC的Co和Fe催化剂。使用廉价的贱金属作为迄今为止使用的Ir和Ru催化剂的替代物似乎是可能的，如与Co的初步工作所示。第三，提出了芳烃选择性加氢和环烷烃脱氢的高效可重复使用催化剂的开发。它们需要通过氢化、ADC和脱氢序列来合成多环N芳族化合物。

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.