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

RUI：基于高价碘化学的新试剂和合成方法的开发

• 批准号: 2243793
• 负责人: Viktor Zhdankin
• 金额: $ 35.73万
• 依托单位: University of Minnesota Duluth
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2243793&HistoricalAwards=false
• 关键词: RUI; Development; New; Reagents; Synthetic

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.

在化学系化学合成项目的支持下，明尼苏达大学杜卢斯（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。 高价碘物质修饰有机化合物的能力，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。这种效用是碘在许多应用中表现得很像过渡金属的结果。对这些相似性的不断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，这个项目是在有机和无机化学的接口，非常适合本科生，研究生和更先进的研究人员，包括工业研究人员。预计该项目将为学生提供高水平的教育和培训，其中许多学生在科学方面的代表性不足。一个新的，无金属，碘介导的反应和探索性的搜索新的和潜在有用的超价试剂的广泛研究提出。具体目标包括：（i）在中性、含水条件下开发假环芳基苯并碘杂硼杂环戊烯作为苯炔前体和高效亲电芳基化试剂，（ii）探索4-碘鎓取代的芳基硼酸作为对苯炔前体，（iii）研究卟啉和二吡咯亚甲基的稳定碘鎓衍生物的合成和反应性，和（iv）寻找通过内部卤素键合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环境友好的化学合成方法，因为它们利用水中的无毒碘化合物作为催化剂或作为可回收/可再循环的试剂。该方法的成功开发将对学术界、制药业、化工业和农业等需要合成有机分子的科学领域产生影响。该奖项反映了NSF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。

项目成果

New Isoxazole‐Substituted Aryl Iodides: Metal‐Free Synthesis, Characterization and Catalytic Activity

新型异恶唑取代芳基碘化物：无金属合成、表征和催化活性

• DOI: 10.1002/ejoc.202301191
• 发表时间: 2024
• 期刊: European Journal of Organic Chemistry
• 影响因子: 2.8
• 作者: Uttam, Bhawna;Zhdankin, Viktor V.;Kumar, Ravi
• 通讯作者: Kumar, Ravi

Pseudocyclic Arylbenziodoxaboroles as Water-Triggered Aryne Precursors in Reactions with Organic Sulfides

• DOI: 10.1021/acs.orglett.4c00197
• 发表时间: 2024-02
• 期刊: Organic Letters
• 影响因子: 5.2
• 作者: A. Yoshimura;Kim Ngo;I. Mironova;Zachary S Gardner;Gregory T. Rohde;Nami Ogura;Akiharu Ueki;M. Yusubov;Akio Saito;V. Zhdankin

Peptide coupling using recyclable bicyclic benziodazolone

• DOI: 10.1039/d3cc04431a
• 发表时间: 2023-12-18
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Uehara，Daigo;Adachi，Sota;Saito，Akio
• 通讯作者: Saito，Akio