Development of an Fe-catalyzed allylic or benzylic C-C-bond activation

在这项工作计划中，提出了在C-C键活化中使用催化量的已定义的富电子铁络合物的概念。稳定而实用的Bu4N[Fe(CO)3(NO)](TBAFe)络合物在烯丙基取代、酯交换或硅氢化反应中得到了广泛的应用，并将作为本研究中的催化剂原型。对本课题组最近发表的铁催化的贫电子乙烯基环丙烷的C-C键活化进行了系统的阐述。虽然到目前为止，富电子铁络合物中的大多数极性乙烯基C-C-键已经被激活，但后续的开发步骤致力于系统地降低C-C-键极性，同时伴随着催化剂-配体体系的优化。作为这一发展的补充，应将反应条件应用于乙烯基环丁烷、-环戊烷或-环己烷的活化。除了这些旨在扩大乙烯基环烷活化的应用范围的研究外，芳基环烷作为一类新的底物也应在标准反应条件下使用。本提案的目的是使用C-C键活化策略获得TBAFe催化的开环反应的详细图像。

In this working program a concept for the use of catalytic amounts of defined electron-rich Fe-complexes in C-C-bond activations is presented. The stable and practical complex Bu4N[Fe(CO)3(NO)] (TBAFe) complex has found frequent use in allylic substitutions, transesterifications or hydrosilylations and shall be used as a catalyst prototype within the present study. The Fe-catalyzed C-C-bond activation of electron-poor vinylcyclopropanes that was recently published by our group shall be elaborated in a systematic manner. While till date mostly polar vinylic C-C-bonds in the present of the electron-rich Fe-complex have been activated subsequent development steps are devoted to a systematic reduction of C-C-bond polarity with concomitant optimization of the catalyst-ligand system. Complementary to this development the reaction conditions shall be applied to the activation of vinylcyclobutanes, -cyclopentanes or -cyclohexanes. Apart from these studies that aim to broaden the application range of the vinylcycloalkane activation arylcycloalkanes as a new class of substrates shall also be employed under the standard reaction conditions. It is the aim of the present proposal to obtain a detailed picture of TBAFe-catalyzed ring-opening reactions using a C-C-bond activation strategy.