I.Iodonium Chemistry. II. Abiological Self-Assembly

I.碘化学。

• 批准号: 6929759
• 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 2008-01-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6929759
• 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（由申请人提供）：本研究的长期目标是开发用于制备复杂分子的有效方法，并开发高度通用和有效的合成工具，以便可以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）碘鎓化合物将被开发为新的，有效的，一般的亲电交叉偶联合作伙伴;（2）将探索配位定向自组装制备大（纳米级），复杂的非生物分子具有明确的形状和大小。具体来说，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，所有化学家都将有概念上的新策略来通过自组装形成（通过非共价合成）大的复杂分子。非生物学自组装策略不仅将提供对自然界自身知之甚少的自组装现象的有价值的见解，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性将促进生产和发现用于诊断和治疗医学疾病的改进和新试剂。系统地研究了芳基、乙烯基和炔基三氟甲磺酸碘鎓盐在交叉偶联反应中的应用。2.检查全氟烷基和全氟芳基碘鎓盐在交叉偶联反应中的应用。3.研究在独特的2D和3D集合的自发自组装中同时使用配位和氢键。4.开发新的、水溶性的、基于配位的自组装策略。通过配位制备和表征新的，不寻常的3D分子物种。6.研究分子识别现象和上述集合体的主客体相互作用，包括生物分子的可能包封。7.研究协同驱动自组装的过程或机制。8.进一步检查碘鎓物质的抗微生物特性和生物活性。9.筛选生物活性，重点是抗肿瘤和抗HIV活性，所有新的，稳定的自组装物种。这些研究是基于我们实验室最近在多价化学和一种新的基于配位的自组装模式上的新发现，而且，所提出的系统作为生物分子受体的支架具有相当大的潜力。