Photoinduced, Copper-Catalyzed C-N Coupling Reactions

光诱导、铜催化的 C-N 偶联反应

• 批准号: 8615873
• 负责人: GREGORY C FU
• 金额: $ 33.53万
• 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/8615873
• 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; 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; public health relevance; 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）：由于大量含氮化合物具有生物活性，因此开发形成C-N键的新方法是有机化学的核心挑战。此外，由于一个分子的两个镜像异构体（“对映体”）通常由于生命分子（如肽、DNA、RNA和碳水化合物）的“手性”而具有不同的生物活性，因此生物医学界需要有效地生成立体异构纯形式的化合物。最后，催化反应的发展是可取的，因为它们通常从效率/经济的角度提供优势。该提案旨在解决所有这三个挑战，特别是发现催化和对映选择性合成含氮化合物的新方法。特别是，该研究计划描述了第一个光诱导、铜催化的C-N键构建方法的发展。预计偶联反应将在异常温和的条件下进行，广泛适用于生成各种含氮化合物家族，并具有良好的立体选择性（如果适用）。此外，该研究计划描述了机理研究（例如，立体化学、质谱、荧光测定和电子顺磁共振光谱），这些研究将深入了解这些光诱导、铜催化的C-N键形成反应的不寻常反应途径，这些反应可能通过自由基中间体进行。