RUI: Development of new polyvalent iodine reagents

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.