RUI: Development of New Reagents and Synthetic Methodologies Based on Hypervalent Iodine Chemistry

在化学系化学合成计划的支持下，明尼苏达大学德卢斯分校(UMD)的Viktor V.zhdankin教授正在研究基于碘的有机化学的新试剂和合成方法的开发。该项目正在探索新的高价碘化合物的制备和基础化学。高价碘物种修饰有机化合物的能力，再加上它们的效率和可持续性，使它们在学术和工业科学家中很有用。这种用途是由于碘在许多应用中的行为非常像过渡金属所致。对这些相似性的持续探索和利用正在导致现代有机化学新的有用方法的发展。更广泛地说，这个项目处于有机化学和无机化学的交界处，非常适合本科生、研究生和更高级的研究人员，包括工业研究人员。该项目预计将为学生提供高水平的教育和培训，他们中的许多人在科学领域的代表性不足。建议对新的、无金属的、碘介导的反应进行广泛的研究，并探索性地寻找新的和潜在有用的高价试剂。具体目标包括：(I)开发作为苯炔前体的伪环芳基苯并碘硼烷化合物和在中性水条件下的高效亲电芳基化试剂，(Ii)探索4-碘取代芳基硼酸作为对苯炔前体，(Iii)研究稳定的卟啉和二吡咯亚甲基碘衍生物的合成和反应活性，以及(Iv)寻找通过内部卤键稳定的新型多价碘化合物。基于这些努力的新的合成方法将有助于发现无害环境的化学合成方法，因为它们利用水中无毒的碘化合物作为催化剂或可回收/可循环的试剂。这一方法的成功发展将对需要合成有机分子的科学领域产生影响，例如在学术界以及制药、化工和农业行业。这一奖项反映了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。

With the support of the Chemical Synthesis Program in the Division of Chemistry, Professor Viktor V. Zhdankin of the University of Minnesota Duluth (UMD) is studying the development of new reagents and synthetic methodologies based on the organic chemistry of iodine. The project is exploring the preparation and fundamental chemistry of new hypervalent iodine compounds. The ability of hypervalent iodine species to modify organic compounds when coupled with their efficiency and sustainability makes them useful among academic and industrial scientists. This utility is the result of iodine behaving much like a transition metal in many applications. The continued exploration and utilization of these similarities is leading to the development of new useful methodologies for modern organic chemistry. More broadly speaking, this project is at the interface of organic and inorganic chemistry and is well-suited for undergraduate, graduate, and more advanced researchers including researchers in industry. The project is expected to provide high level of education and training for students, many of whom are underrepresented in science. A broad study of new, metal-free, iodine-mediated reactions and an exploratory search for new and potentially useful hypervalent reagents is proposed. Specific objectives include: (i) the development of pseudocyclic arylbenziodoxaboroles as benzyne precursors and highly efficient electrophilic arylating reagents under neutral, aqueous conditions, (ii) the exploration of 4-iodonium substituted arylboronic acids as para-benzyne precursors, (iii) the study of the synthesis and reactivity of stabilized iodonium derivatives of porphyrins and dipyrromethenes, and (iv) the search for new types of polyvalent iodine compounds that are stabilized by internal halogen bonding. New synthetic methodologies based on these efforts will contribute to the discovery of environmentally benign methods for chemical synthesis as they utilize non-toxic iodine compounds in water as catalysts or as recoverable/recyclable reagents. The successful development of this methodology will have an impact on the areas of science where the synthesis of organic molecules is required, such as in academia and in the pharmaceutical, chemical, and agricultural industries.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.