Correlation of electronic structure to iron catalyzed C-H bond functionalization

电子结构与铁催化C-H键功能化的相关性

基本信息

批准号：
9115643
负责人：
Theodore A Betley
金额：
$ 32.4万
依托单位：
HARVARD UNIVERSITY
依托单位国家：
美国
项目类别：
财政年份：
2015
资助国家：
美国
起止时间：
2015-08-01 至 2019-03-31
项目状态：
已结题

项目摘要

DESCRIPTION (provided by applicant): Correlation of electronic structure to iron catalyzed C-H bond functionalization In the field of homogenous catalysis, few reports have appeared offering general, chemically mild methods for the introduction of nitrogen- or oxygen-containing functional groups into simple hydrocarbon substrates. The ability to selectively incorporate functionality into unactivated C-H bonds represents a significant advance in converting inexpensive chemical feed stocks (e.g. hydrocarbons) to value-added functional molecules. However, the oxidative substitution of C-H bonds with amines or other functional groups often requires preoxidation of substrate or employs strong chemical oxidants in concert with atom or group transfer processes. A streamlined synthesis for functionalized products (e.g. N-heterocycles) with minimal or complete absence of waste generation would have tremendous impact on the synthesis of fine chemicals and pharmaceuticals. Towards this end, we have synthesized a class of electrophilic complexes featuring transiently-formed, or metastable metal-ligand multiple bonds capable of mediating C-H bond functionalization. Using dipyrrin ligand platforms as truncated models of the porphyrin platform found in P450 hydroxylase enzymes, we have observed reactivity from the ferrous-ligand constructs mirrors their porphyrin analogues. Catalytic C-H bond amination and olefin aziridination have been observed from the reaction of organic azides with simple iron(II) and iron(I) coordination complexes. The iron-catalyzed amination reaction is tolerant to a variety of organic azide precursors and has shown reactivity with a range of organic substrates to form N- heterocyclic products: linear azides can be intramolecularly aminated to form both pyrrolidine and piperidine structures, bearing an array of a-functional groups. The broader scientific impact of the proposed research can be summarized as the following: we will improve our understanding of factors contributing to the promotion of productive C-H bond activation and functionalization, further developing new classes of inorganic/organometallic catalysts to synthesize value-added commodity chemicals via clean reaction routes with minimal waste product.

描述（通过施用）：电子结构与均质催化的C-H键功能化的相关性是，很少有报道出现了一般的化学方法，用于引入氮或氧气氧气碳酸氢碳纤维的能力。 c-h键呈液位液含量，而氧化物（例如，碳氢化合物）到值地址分子中，C-H键或其他功能性群体通常需要与原子或组转移过程中的底物或emplanters一起预氧化。随着对精细化学的巨大影响的浪费产生的最小或紧凑，我们已经合成了具有跨形成的IAT形成的C-H键功能化的植物络合物。用简单的铁（II）和铁（I）协调复合物的有机叠氮化物的CTION宽容。为了形成吡咯氨酸和尖端的结构，可以将拟议研究的更广泛的科学影响总结为以下OND激活和功能化，进一步开发了新的无机/器官分析类别的新类别通过最小废物的清洁反应路线进行麦克拉。