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

点击翻译按钮获取中文摘要

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.