SusChEM: CAREER: Synthesis of Macrocyclic Carbene Complexes for Catalytic Aziridination

SusChEM：职业：催化氮丙啶化大环卡宾配合物的合成

• 批准号: 1254536
• 负责人: David Jenkins
• 金额: $ 65万
• 依托单位: University of Tennessee Knoxville
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-05-01 至 2019-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1254536&HistoricalAwards=false
• 关键词: SusChEM; CAREER; Synthesis; Macrocyclic; Carbene

The Chemical Catalysis Program of the NSF Division of Chemistry supports the research efforts of Professor David M. Jenkins of the University of Tennessee at Knoxville (UTK) to explore new aziridination reactions using organic azides (both aryl and alkyl variants) as the nitrene source and alkenes as the carbon source. This innovative reaction involves novel transition metal complexes supported by strong sigma-donor macrocyclic tetra-N-heterocyclic carbenes (NHCs) as auxiliary ligands which act as homogeneous azirdination catalysts. The research is accomplished in four steps: ligation of tetracarbenes to first and second row transition metals (especially iron), catalytic studies of aziridination reactions between organic azides and alkenes, mechanistic studies of the reaction through probes of intermediates (i.e., metal imide complexes), and expansion of substrate scope to make the reactions relevant to industrial, pharmaceutical, and biological applications. The broader impacts of this work include providing opportunities for pre-college scholars from Central High School (CHS), an economically-disadvantaged high school in Knoxville, TN, to perform research at the UTK. With the assistance of high school teachers at CHS and collaborators in the Knox County School District, new Advanced Placement (AP) laboratories that match Professor Jenkins's research interests are being developed within the guidelines of the AP Chemistry curriculum. The laboratory capabilities at CHS are being upgraded in order to support the new experiments. Finally, in addition to the typical technical presentations and publications, these research results are being disseminated though the Pre-Game Showcase at UTK football games.Aziridine compounds are found in natural products, such as mitomycins and azinomycins, that have antitumor and antibiotic properties crucial to the development of new pharmaceutical products. Despite the myriad of uses, the synthesis of aziridine compounds has been wasteful and expensive due to the need for additional reagents that are not fully used in the final products. This CAREER project utilizes less expensive metal-based catalytic processes to avoid the need for expensive reagents. The improved reactions are expected to have impact in biology and synthetic organic chemistry, particularly in the preparation of new medicines. In his work with teachers and administrators at Central High School in Knoxville, Tennessee, Professor Jenkins stresses the use of sustainable processes in the development of new laboratories for the Advanced Placement (AP) Chemistry courses. Professor Jenkins publishes his work in technical journals but also disseminates his group's results in non-traditional forums, such as the Pre-Game Showcase at the University of Tennessee Knoxville football games.

美国国家科学基金会化学部的化学催化项目支持大卫教授的研究工作。Tennessee大学诺克斯维尔分校（UTK）的Jenkins等人开发了使用有机叠氮化物（芳基和烷基变体）作为氮宾源和烯烃作为碳源的新的氮杂环丙烷化反应。 该创新反应涉及由强σ-供体大环四-N-杂环卡宾（NHC）作为辅助配体支撑的新型过渡金属络合物，其充当均相氮杂环化催化剂。 本研究分四步完成：四碳烯与第一、第二行过渡金属（特别是铁）的配位反应，有机叠氮化物与烯烃的氮丙啶化反应的催化研究，通过中间体（即，金属酰亚胺络合物），以及扩大底物范围以使反应与工业、制药和生物应用相关。 这项工作的更广泛的影响，包括提供机会，从中央高中（CHS），在诺克斯维尔，TN的经济上处于不利地位的高中大学前学者，在UTK进行研究。 在CHS的高中教师和诺克斯县学区的合作者的协助下，与詹金斯教授的研究兴趣相匹配的新的高级安置（AP）实验室正在AP化学课程的指导方针内开发。 目前正在提升中心的实验室能力，以支持新的实验。 最后，除了典型的技术演示和出版物，这些研究成果还通过UTK足球赛的赛前展示进行传播。氮丙啶化合物存在于天然产物中，如丝裂霉素和azinomycins，具有抗肿瘤和抗生素特性，对新药物的开发至关重要。 尽管有无数的用途，氮丙啶化合物的合成是浪费和昂贵的，因为需要在最终产物中未完全使用的额外试剂。 这个CAREER项目利用较便宜的金属基催化工艺，以避免对昂贵试剂的需求。 改进的反应预计将在生物学和合成有机化学中产生影响，特别是在制备新药方面。 在他的工作与教师和管理人员在中央高中诺克斯维尔，田纳西州，教授詹金斯强调在先进的安置（AP）化学课程的新实验室的发展中使用可持续发展的过程。 詹金斯教授在技术期刊上发表他的研究成果，但也在非传统论坛上传播他的小组的成果，例如田纳西大学诺克斯维尔足球赛的赛前展示。