RUI: Development of new polyvalent iodine reagents

在这项由化学系化学合成计划支持的项目中，明尼苏达大学德卢斯大学化学和生物化学系的Viktor V.zhdankin教授正在开发新类型的氧化剂。氧化剂是构建各种分子的重要工具。Zzhdankin教授和他的团队正在开发的方法使用多价碘化合物，因为它们比目前使用的试剂更有效，更环保。基于碘的体系之所以有效，是因为碘是元素周期表中被归类为非金属的最重元素之一。因此，这些更可持续的试剂模仿了它们所用来取代的重的、往往有毒的过渡金属的结构特征和反应模式。同样重要的是要注意到，这些试剂是新的。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。该项目位于有机化学和无机化学的交界处，非常适合本科教育和各级科学家的培养。张丹金教授所在的团队为在科学领域代表性不足的学生提供最高水平的教育和培训，这一点由来已久。张丹金教授和他的团队正在进行一项新的、无金属的、由碘介导的反应的广泛研究。在这一努力中，他们正在寻找新的高价试剂，他们正在探索这些试剂使之能够发生的反应的新模式。该项目的具体目标包括研究芳基苯并碘氧硼化合物作为有效的苯基前体，开发基于酚性碘盐的新的卡宾前体，研究酚性二芳碘盐的芳基化反应，以及研究磷-碘叶立德作为合成三氟甲基取代烯烃的试剂。在第二项工作中，张丹金教授正在寻找稳定的和潜在有用的高价碘与中离子卡宾的络合物。基于有机高价碘化学的新合成方法正在为环境友好的化学合成方法做出贡献，因为它使用无毒的碘化合物作为催化剂或水溶液中的可回收试剂。这一方法论的成功发展对如何合成与制药、化工和农业相关的分子产生了影响。该项目为所有教育层次的学生提供了极好的培训，包括那些来自历史上在科学界代表性不足的群体的学生。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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.