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，并将其用作合成胺的创新方法的催化剂。这些研究将主要集中在两个有工业前景的转化上：烯烃、1，3-二烯和苯乙烯的氢氨烷化反应以及炔烃和烯烃的氢胺化反应。对于这两个反应，设想揭示详细的结构-活性-关系，以便确定显著改进的催化剂，例如，具有更高的活性和/或更好的选择性。在烯烃、1，3-二烯和苯乙烯的分子间氢氨烷基化反应中，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，还将尝试控制区域选择性，以利于工业上重要的线性产物，并首次实现炔烃和烯的相应反应。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于确定活性更高的新催化剂。该项目这一部分的长期目标是实现非活性烯烃的分子间氢胺化反应。最后，还将启动对其他催化过程的相应研究。

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.