Photoinduced, Copper-Catalyzed C-N Coupling Reactions

光诱导、铜催化的 C-N 偶联反应

• 批准号: 9020981
• 负责人: GREGORY C FU
• 金额: $ 35.51万
• 依托单位: CALIFORNIA INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-05-15 至 2018-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/9020981
• 关键词: Address; Biochemistry; Biological; Biology; Carbohydrates; Chemicals; Communities; Complement; Complex; Copper; Coupling; DNA; Development; Discipline; Electron Spin Resonance Spectroscopy; Exhibits; Family; Fluorometry; Generations; Handedness; Health; Image; Investigation; Isomerism; Life; Mass Spectrum Analysis; Methods; Nitrogen; Organic Chemistry; Organic Synthesis; Pathway interactions; Peptides; Pharmaceutical Chemistry; Process; RNA; Reaction; Research; Transition Elements; aryl halide; base; catalyst; computer studies; enantiomer; insight; novel strategies; tool

DESCRIPTION (provided by applicant): Because a wide array of nitrogen-containing compounds exhibit bioactivity, the development of new methods for the formation of C-N bonds is a central challenge in organic chemistry. Furthermore, because the two mirror-image isomers ("enantiomers") of a molecule generally have different biological activity due to the "handedness" of the molecules of life (e.g., peptides, DNA, RNA, and carbohydrates), there is a need in the biomedical community to efficiently generate compounds in stereoisomerically pure form. Finally, the development of catalyzed reactions is desirable, since they often offer advantages from the standpoints of efficiency/economy. This proposal is directed at addressing all three of these challenges, specifically, the discovery of new methods for the catalytic and enantioselective synthesis of nitrogen-containing compounds. In particular, the research plan describes the development of the first photoinduced, copper-catalyzed methods for the construction of C-N bonds. The coupling reactions are anticipated to proceed under unusually mild conditions, to have broad applicability for the generation of diverse families of nitrogen-containing compounds, and to proceed with good stereoselectivity (when applicable). Furthermore, the research plan describes mechanistic studies (e.g., stereochemical, mass spectrometry, fluorometry, and electron paramagnetic resonance spectroscopy) that will provide insight into the unusual reaction pathway of these photoinduced, copper-catalyzed C-N bond-forming reactions, which likely proceed through a radical intermediate.

描述（由申请人提供）：因为多种含氮化合物表现出生物活性，所以开发形成C-N键的新方法是有机化学的核心挑战。此外，由于分子的两个镜像异构体（“对映异构体”）通常由于生命分子（例如肽，DNA，RNA和碳水化合物）而具有不同的生物学活性，因此有需要在生物医学群落中，以立体异构形式有效生成化合物。最后，需要催化反应的发展，因为它们通常从效率/经济的角度提供优势。该建议旨在解决所有这三个挑战，特别是发现了含氮化合物的催化和对映选择性合成的新方法。特别是，该研究计划描述了第一个光诱导的铜催化方法的开发，用于构建C-N键。预计将在异常温和的条件下进行耦合反应，以广泛适用于含氮化合物的不同家族，并具有良好的立体选择性（如果适用）。此外，研究计划还描述了机械研究（例如，立体化学，质谱法，荧光法和电子顺磁共振光谱法）将提供对这些光诱导的，铜催化的C-N键反应的异常反应途径的洞察力，可能通过根治性中间体。