SusChEM: RUI: Organohypervalent Iodine Chemistry

在这个由化学系化学合成计划资助的项目中，明尼苏达大学德卢斯大学化学和生物化学系的Viktor V.zhdankin教授将探索三价和五价碘化合物的化学，这是一种高效和环境友好的氧化剂，在有机合成中有着广泛的应用。虽然有机高价碘化合物是公认的化学计量试剂，但在高价碘促进的新催化反应的开发方面进展甚微。提出了基于高价碘化学的新的、无金属的催化反应的研究，以及对新的和潜在有用的有机高价碘化合物的探索性探索。基于新的、碘代芳烃催化的氧化转化，例如酰胺的Hofmann重排为胺，以及导致异恶唑衍生物和N-取代吲哚的氧化杂环化反应，将被研究。还将研究有机碘催化的不对称氮杂环化反应，该反应是在最近发现的以有机碘为催化剂的无金属烯烃氮杂环化反应的基础上进行的。还将对新的、有潜在应用价值的高价碘酰胺、亚胺和叶立德的制备、结构表征和化学性质进行探索性研究。基于有机高价碘化学的新合成方法将有助于环境友好的化学合成方法，因为它使用无毒的碘化合物作为催化剂或水溶液中可回收的试剂。这一方法学的成功发展将对任何需要合成分子的活动领域产生影响，例如制药、化工、农业以及生物和化学研究活动。此外，该项目将为学生提供极好的培训，从本科前到博士后，包括那些在科学界历来代表性不足的学生。

In this project funded 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 will explore the chemistry of trivalent and pentavalent iodine compounds, which are efficient and environmentally benign oxidizing reagents with numerous applications in organic synthesis. While organohypervalent iodine compounds are well-established stoichiometric reagents, little progress has been made in the development of new catalytic reactions promoted by hypervalent iodine. Studies of new, metal-free catalytic reactions based on hypervalent iodine chemistry and an exploratory search for new and potentially useful organohypervalent iodine compounds are proposed. Synthetically useful methodologies based on the new, iodoarene-catalyzed oxidative transformations, such as the Hofmann rearrangement of amides to amines and the oxidative heterocyclization reactions leading to isoxazole derivatives and N-substituted indoles, will be investigated. Organoiodine-catalyzed enantioselective aziridination reactions on the basis of a recently discovered metal-free catalytic procedure for the aziridination of alkenes using organic iodide as catalyst will also be studied. An exploratory study on the preparation, structural characterization, and chemical properties of new, potentially useful hypervalent iodine amides, imides, and ylides will be also performed.New synthetic methodology based on organohypervalent iodine chemistry will contribute 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 will have an impact on any area of activity in which the synthesis of molecules is needed, such as the pharmaceutical, chemical, agricultural industry, and the biological and chemical research activities. In addition, this project will provide excellent training of students, from pre-undergraduate to post-doctoral, including those from groups historically underrepresented in the sciences.