Development of Fe-catalyzed non-oxidative C-H-aminations

基于我们在Bu4N[Fe(CO)3(NO)]-催化的C(sp2)- h -和C(sp3)- h键的分子内胺化领域报告的结果，该项目描述了一个计划，旨在系统地将该反应扩展到在分子内和分子间使用烷基化剂的C(sp2)- h -和C(sp3)- h键的胺化。芳香底物的直接分子间胺化为芳胺提供了一种有效的途径，但在铁催化领域，这种转化尚不发达。研究的目的是系统地确定适合这种转化的叠氮化物，这将在随后的芳香底物定向胺化研究中使用。为了达到高度的正交选择性，将使用不同的定向基团。这是本研究项目的最终目标是制定一个协议的分子间胺化的非功能化烷烃。这一领域以及相应的以铁为催化剂的定向或非定向芳香族c - h胺化反应领域尚未开发。

Based on results that we reported in the field of Bu4N[Fe(CO)3(NO)]-catalyzed intramolecular aminations of C(sp2)-H- and C(sp3)-H-bonds using arylazides (C(sp2Ar)-N3) the project describes a programme aiming to systematically expand this reaction to the amination of C(sp2)-H- and C(sp3)-H-bond using alkylazides both in an intra- and intermolecular fashion. The direct intermolecular amination of aromatic substrates offers an efficient access to arylamines, however in the field of Fe-catalysis this transformation is underdeveloped. The investigations aim to systematically identify appropriate azides for this kind of transformation, which shall be employed in subsequent studies in the directed amination of aromatic substrates. Different directing groups will be used in order to achieve a high degree of ortho-selectivity. It is the ultimate goal of this research project to develop a protocol for the intermolecular amination of non-functionalized alkanes. This field and the corresponding field of the directed or non-directed aromatic C-H-amination using Fe-catalysts is yet unexplored.