I.Iodonium Chemistry. II. Abiological Self-Assembly

描述（由申请人提供）：本研究的长期目标是开发制备复杂分子的有效方法，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、一般的亲电交叉偶联伙伴；(2)协同定向自组装将探索制备具有明确形状和大小的大型（纳米级）复杂的非生物分子。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性的新策略来通过自组装形成（通过非共价合成）大型复杂分子。非生物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，对所有生物体都很重要，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随时可用性将有助于生产和发现用于诊断和治疗医学疾病的改进和新的制剂。该项目的具体目标是：1。系统地研究了芳基、乙烯基和炔基三氟酸盐在交叉偶联反应中的应用。2. 研究全氟烷基和全氟芳基碘盐在交叉偶联反应中的应用。3. 检查同时使用的配合和氢键在自发组装独特的2D和3D集成。4. 开发新的，水溶性的，基于协调的，自组装的策略。通过配位制备和表征新的，不寻常的三维分子物种。6. 研究上述系统的分子识别现象和主客相互作用，包括可能的生物分子包封。7. 研究协调驱动自组装的过程或机理。8. 进一步研究了碘的抗菌特性和生物活性。9. 生物活性筛选，重点是抗肿瘤和抗hiv活性，所有新的，稳定的自组装物种。提出的研究是基于最近的新发现，在我们的实验室在多价化学和一个新的基于配位的自组装范式。此外，所提出的系统具有相当大的潜力作为支架的生物分子受体的创造。

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.