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

Fe催化烯丙基或苄基C-C键活化的发展

• 批准号: 254650899
• 负责人: Professor Dr. Bernd Plietker
• 金额: --
• 依托单位: Professur für Organische Chemie I
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/254650899?language=en
• 关键词: Development; Fe; catalyzed; allylic; benzylic

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.

在这个工作计划中，提出了在C-C键活化中使用催化量的定义的富电子Fe络合物的概念。Bu_4N [Fe（CO）_3（NO）]（TBAFe）配合物在烯丙基取代反应、酯交换反应和硅氢加成反应中有着广泛的应用，可作为催化剂原型。对本课题组最近发表的铁催化贫电子乙烯基环丙烷的C-C键活化反应进行了系统的阐述。虽然迄今为止，在富电子铁配合物的存在下，大多数极性乙烯基C-C键已被激活，但后续的开发步骤致力于系统地降低C-C键极性，同时优化催化剂-配体系统。补充这一发展的反应条件应适用于乙烯基环丁烷，环戊烷或环己烷的活化。除了这些旨在拓宽乙烯基环烷烃活化的应用范围的研究外，芳基环烷烃作为一类新的底物也应该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。

项目成果

Insertion of Imines into Vinylcyclopropanes Catalyzed by Nucleophilic Iron Complexes: A Formal [3+2]-Cycloaddition Strategy for the Synthesis of Substituted Pyrrolidine Derivatives

• DOI: 10.1055/s-0034-1379180
• 发表时间: 2014-09
• 期刊: Synlett
• 影响因子: 2
• 作者: Dominik Pursley;B. Plietker