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Palladium and Nickel Catalyzed C-H Activation/C-C Bond Formation

钯和镍催化的 C-H 活化/C-C 键形成

基本信息

批准号：
8574624
负责人：
Dipannita Kalyani
金额：
$ 28.06万
依托单位：
ST. OLAF COLLEGE
依托单位国家：
美国
项目类别：
财政年份：
2013
资助国家：
美国
起止时间：
2013-09-01 至 2017-08-31
项目状态：
已结题

项目摘要

DESCRIPTION (provided by applicant): The overall goal of the proposed research is the development of general, efficient and cost-effective methods for the conversion of C-H bonds to C-C bonds. The products of the proposed transformations are structural motifs prevalent in biologically active molecules. The proposed methods have the potential to serve as cost-effective and environmentally friendly alternatives to the currently known methods for the strategic introduction of C-C bonds in the context of synthesis of medicinal drugs. Specifically this proposal seeks to develop palladium- and nickel-catalyzed methods for the construction of C-C bonds. The successful implementation of the research described herein will lead to novel intra- and intermolecular arylation of arene and alkyl C-H bonds. Aim 1 seeks to develop palladium-catalyzed methods for the direct arylation of C-H bonds using phenolic electrophiles. The transformation will be a significant advance over the known methods for C-H arylations, the majority of which employ aryl halides as electrophiles. The use of inexpensive and readily accessible phenolic electrophiles render these transformations, more environmentally friendly than previously reported direct arylation methods. Aims 2 and 3 are focused on the development of Ni-catalyzed direct arylation of C-H bonds. The use of earth abundant and inexpensive nickel catalysts will be significantly more cost effective than previously known methods, many of which utilize precious noble metal catalysts. The most significant challenge toward the accomplishment of the Ni-catalyzed arylations is the dearth of mechanistic understanding for C-H activation at a Ni center, a key step of the proposed transformations. As such the development of the Ni-catalyzed direct arylations is based on careful consideration of the mechanistic aspects of related well-studied Pd-catalyzed C-H arylations. Additionally, the research design includes fundamental-mechanistic investigations of the Ni-catalyzed arylations. These studies will aid in the accomplishment of the proposed work and will enable the discovery of other synthetically useful Ni-catalyzed C-H functionalizations. The PI's research group has enhanced the research environment at St. Olaf College, providing a unique opportunity to expose undergraduates to the cutting edge of organometallic research. The current proposal will provide the students with relevant experience and a foundation in the techniques used in both pharmaceutical and biomedical research at the next level.

描述（由申请人提供）：拟议研究的总体目标是开发通用、高效且具有成本效益的C-H键转化为C-C键的方法。所提出的转化的产物是生物活性分子中普遍存在的结构基序。所提出的方法有可能作为成本效益和环境友好的替代方案，目前已知的方法的战略引入的C-C键的背景下，合成的医药。具体而言，该提案旨在开发用于构建C-C键的钯和镍催化方法。本文所述研究的成功实施将导致芳烃和烷基C-H键的新型分子内和分子间芳基化。目的1：发展钯催化的酚类亲电试剂直接芳基化C-H键的方法。这种转化将是对已知的C-H芳基化方法的重大进步，其中大多数采用芳基卤化物作为亲电试剂。使用廉价和容易获得的酚类亲电试剂使这些转化比以前报道的直接芳基化方法更环保。目标2和3集中于Ni催化的C-H键的直接芳基化的发展。使用地球丰富和廉价的镍催化剂将比以前已知的方法显著地更具成本效益，其中许多方法使用贵重的贵金属催化剂。实现Ni催化芳基化反应的最大挑战是缺乏对Ni中心C-H活化的机理理解，这是所提出的转化的关键步骤。因此，镍催化的直接芳基化反应的发展是基于仔细考虑相关的研究充分的钯催化的C-H芳基化反应的机理方面。此外，研究设计包括镍催化芳基化反应的基本机理研究。这些研究将有助于完成所提出的工作，并将使其他合成有用的Ni催化的C-H官能化的发现。PI的研究小组增强了圣奥拉夫学院的研究环境，为本科生接触有机金属研究的前沿提供了独特的机会。目前的建议将为学生提供相关的经验和基础，在制药和生物医学研究中使用的技术在下一个层次。