RUI: Development of new polyvalent iodine reagents

在化学学部化学合成项目的支持下，明尼苏达大学德卢斯分校化学与生物化学系的Viktor V. Zhdankin教授正在开发新型氧化剂。氧化剂是构建各种分子的重要工具。Zhdankin教授和他的团队正在开发的方法利用多价碘化合物，因为它们比目前使用的试剂更有效，更环保。基于碘的系统之所以有效，是因为碘是元素周期表中被列为非金属的最重元素之一。因此，这些更可持续的试剂模仿结构特征和反应模式的重，经常有毒的过渡金属，他们被用来取代。同样重要的是要注意试剂是新的。因此，它们不仅可以用来复制现有的方法，还可以用来开发全新的反应。本项目处于有机化学与无机化学的交叉领域，既适合本科教学，也适合各级科研人员的培养。Zhdankin教授的小组长期以来一直为科学领域代表性不足的学生提供最高水平的教育和培训。Zhdankin教授和他的团队正在对新的、无金属的、碘介导的反应进行广泛的研究。在这项工作中，他们正在寻找新的高价试剂，他们正在探索这些试剂所能实现的新反应模式。该项目的具体目标包括：研究芳基苯并碘多溴醚作为有效的苯前体，开发基于酚类碘盐的新型碳前体，研究与酚类二芳基碘鎓盐的芳基化反应，以及研究磷-碘酰化物作为合成三氟甲基取代烯烃的试剂。在第二次努力中，Zhdankin教授正在寻找稳定的、可能有用的高价碘与介离子碳烯的配合物。基于有机高价碘化学的新合成方法是一种环境友好的化学合成方法，因为它利用无毒的碘化合物作为催化剂或水溶液中的可回收试剂。这种方法的成功发展对如何合成与制药、化学和农业工业相关的分子产生了影响。该项目为各级教育的学生提供了优秀的培训，包括那些来自历史上在科学领域代表性不足的群体的学生。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

In this project supported by the Chemical Synthesis Program of the Chemistry Division, Professor Viktor V. Zhdankin of the Department of Chemistry and Biochemistry at University of Minnesota Duluth is developing new classes of oxidizing agents. Oxidizing agents are important tools for the construction of a wide variety of molecules. The approach Professor Zhdankin and his group is developing utilizes polyvalent iodine compounds because they are efficient and environmentally more "friendly" that the reagents currently used. The iodine based systems work because iodine is one of the heaviest elements in the Periodic Table classified as a non-metal. Hence, these more sustainable reagents mimic the structural features and reactivity pattern heavy, frequently toxic transition metals they are being used to replace. It is also important to note that the reagents are new. As such, they can be used to not only replicate existing methods, but also to develop entirely new reactions. The project lies at the interface of organic and inorganic chemistry and it is well suited for undergraduate education as well as for training of scientists at all levels. Professor Zhdankin's group has a long history of providing the highest level of education and training for students underrepresented in science. Professor Zhdankin and his group are pursuing a broad study of new, metal-free, iodine-mediated reactions. In this effort, they are searching for new hypervalent reagents, and they are exploring the new modes of reactivity those reagents enable. Specific objectives of this project include the study of arylbenziodoxaboroles as efficient benzyne precursors, the development of new carbene precursors based on phenolic iodonium salts, the study of arylation reactions with phenolic diaryliodonium salts, and the study of phosphonium-iodonium ylides as reagents for synthesis of trifluoromethyl-substituted alkenes. In a second effort, Professor Zhdankin is searching for stable and potentially useful hypervalent iodine complexes with mesoionic carbenes. The new synthetic methodology based on organohypervalent iodine chemistry is contributing to environmentally benign methods for chemical synthesis as it utilizes non-toxic compounds of iodine as catalysts or recyclable reagents in aqueous solutions. Successful development of this methodology is having an impact on how the synthesis of molecules relevant to the pharmaceutical, chemical, and agricultural industries is approached. This project provides excellent training to students at all levels of education including those from groups historically underrepresented in the sciences.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.