Metal-Catalyzed Amine Syntheses Using Aminoheteroaromatics as Ligand Precursors

该项目的目的是从2-氨基吡啶或相应的氨基杂芳烃合成早期过渡金属配合物，并将其作为创新合成胺方法的催化剂。研究将主要集中在两个工业上有前景的转化：烯烃、1,3-二烯和苯乙烯的氢胺烷基化以及炔烃和烯烃的氢胺化。对于这两种反应，期望揭示详细的结构-活性-关系，以确定显著改进的催化剂，例如活性增加和/或选择性更好。就烯烃、1,3-二烯和苯乙烯的分子间氢胺烷基化而言，一个主要目标是扩大该过程的范围，以便实现伯胺、二烷基胺以及1,1-和1,2-二取代烯烃的有效反应。此外，将尝试控制区域选择性，有利于工业上重要的线性产物，并首次实现相应的炔和烯的反应。关于烯烃和炔烃的氢胺化反应的平行和大多数类似的研究将主要集中在鉴定具有改进活性的新催化剂上。该项目的长期目标是实现非活化烯烃的分子间氢胺化反应。最后，还将对其他催化工艺进行相应的研究。

The aim of the project is to synthesize early transition metal complexes from 2-aminopyridines or corresponding aminoheteroaromatics and to use them as catalysts for innovative methods for the synthesis of amines. The investigations will mainly focus on two industrially promising transformations: the hydroaminoalkylation of alkenes, 1,3-dienes and styrenes as well as the hydroamination of alkynes and alkenes. For both reactions, it is envisioned to reveal detailed structure-activity-relationships in order to identify significantly improved catalysts, e.g. with increased activity and/or better selectivity. In the case of the intermolecular hydroaminoalkylation of alkenes, 1,3-dienes and styrenes, one major goal is to expand the scope of the process in order to achieve efficient reactions of primary amines, dialkyl amines as well as 1,1- and 1,2-disubstituted alkenes. In addition, it will be attempted to control the regioselectivity in favor of the industrially important linear products and to achieve corresponding reactions of alkynes and allenes for the first time. Parallel and mostly analogous studies dealing with the hydroamination of alkenes and alkynes will mainly focus on the identification of new catalysts with improved activity. The long term goal of this part of the project is to achieve intermolecular hydroamination reactions of non-activated alkenes. Finally, corresponding studies will also be initiated for additional catalytic processes.