I.Iodonium Chemistry. II. Abiological Self-Assembly

I.碘化学。

• 批准号: 6789921
• 负责人: Peter J Stang
• 金额: $ 30万
• 依托单位: UNIVERSITY OF UTAH
• 依托单位国家: 美国
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-01-01 至 2006-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6789921
• 关键词: alkynes; antiinfective agents; antineoplastics; chemical addition; chemical synthesis; drug screening /evaluation; esters; halogenation; hydrogen bond; iodine; molecular assembly /self assembly; stereochemistry

DESCRIPTION (provided by applicant): The long term objective of this research is to develop efficient methods for the preparation of complex molecules, and develop highly versatile and efficient synthesis tools so that any desired molecule may be prepared in a practical manner. Two different approaches will be investigated: (1) iodonium compounds will be developed as new, efficient, general electrophilic cross-coupling partners; (2) coordination directed self-assembly will be explored to prepare large (nanoscale), complex abiological molecules with well defined shapes and size. Specifically, organic chemists will have new reagents for the formation of a variety of structurally demanding C-C bonds and all chemists will have conceptually new strategies for the formation (via noncovalent synthesis) of large, complex molecules via self-assembly. Abiological self-assembly strategies will provide not only valuable insights into nature's own poorly understood self-assembly phenomen, of importance in all living organisms, but will also find many useful applications in molecular recognition, selective substrate transformations, sensing, signal transduction and many other, yet unforeseen, biomedical uses. In the long term, the ready availability of new synthesis methodologies that we are developing will facilitate the production and discovery of improved and new agents for the diagnosis and treatment of medical disorders.Specific aims for the project are: 1. Systematically investigating the use of aryl-, vinyl- and alkynyliodonium triflates in cross coupling reactions. 2. Examining the use of perfluoroalkyl and perfluoroaryl iodonium salts in cross coupling reactions. 3. Examine the simultaneous use of coordination and hydrogen bonding in the spontaneous self-assembly of unique 2D and 3D ensembles. 4. Developing new, water soluble, coordination based, self-assembly strategies.5. Preparing and characterizing new, unusual 3D molecular species via coordination. 6. Investigating molecular recognition phenomena and host-guest interactions of the above ensembles, including the possible encapsulation of biological molecules. 7. Study the process or mechanism of coordination driven self assembly. 8. Further examining the antimicrobial properties and biological activity of iodonium species. 9. Screening for biological activity, with emphasis on antitumor and anti-HIV activity, all new, stable self-assembled species. The proposed studies are based upon recent, new discoveries in our laboratories on polyvalent chemistry and a novel coordination based self-assembly paradigm.Moreover, the proposed systems have considerable potential as scaffolds for the creation of biomolecular receptors.

描述(申请人提供)：这项研究的长期目标是开发有效的方法来制备复杂分子，并开发高度通用和高效的合成工具，以便以实用的方式制备任何所需的分子。将研究两种不同的方法：(1)碘化合物将被开发为新的、高效的、通用的亲电交叉偶联伙伴；(2)将探索配位定向自组装以制备形状和尺寸定义良好的大的(纳米级)、复杂的非生物分子。具体地说，有机化学家将有新的试剂来形成各种结构要求高的C-C键，所有的化学家将有概念上的新策略来通过自组装形成大的、复杂的分子(通过非共价合成)。非生物自组装策略不仅将提供对自然界本身鲜为人知的自组装现象的有价值的见解，这在所有生物体中都是重要的，而且还将在分子识别、选择性底物转化、传感、信号转导和许多其他尚未预见的生物医学用途中找到许多有用的应用。从长远来看，我们正在开发的新合成方法的现成可用将有助于生产和发现用于诊断和治疗医学疾病的改进的和新的试剂。该项目的具体目标是：1.系统地研究芳基、乙烯基和炔基三氟化碘在交叉偶联反应中的用途。2.考察了全氟烷基和全氟芳基碘盐在交叉偶联反应中的应用。3.研究配位和氢键在独特的2D和3D系综的自发自组装中的同时使用。4.开发新的、水溶性的、基于协调的、自组装的战略。通过配位制备和表征新的、不同寻常的3D分子物种。6.研究上述系综的分子识别现象和主客体相互作用，包括可能的生物分子的包裹。7.研究协调驱动的自组装过程或机理。8.进一步检查碘物种的抗菌性能和生物活性。9.筛选生物活性，重点是抗肿瘤和抗艾滋病毒活性，所有新的、稳定的自组装物种。建议的研究是基于我们实验室最近在多价化学方面的新发现和一种新的基于配位的自组装范例。此外，建议的系统作为创建生物分子受体的支架具有相当大的潜力。