Novel Synthetic Methods

新的合成方法

• 批准号: 1955663
• 负责人: Vladimir Gevorgyan
• 金额: $ 44万
• 依托单位: University of Texas at Dallas
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955663&HistoricalAwards=false
• 关键词: Novel; Synthetic; Methods

With this award, the Chemical Synthesis Program of the NSF Division of Chemistry is supporting the research of Professor Gevorgyan. His research team is developing novel methods for converting abundant and cheap feedstock materials into value-added products. Carbon-hydrogen bonds plentifully present in organic molecules are targeted for useful elaboration. However, the high strength of the carbon-hydrogen bond prevents its easy breakage and thus may require forcing conditions such as high reaction temperatures, or the use of precious and rare transition metals. Such chemistry may also require the use of highly unstable reagents, which then raise safety concerns. Professor Gevorgyan’s team is investigating very mild and safe transition metal-free methods for generation and manipulation of various reactive species from simple and stable precursors under visible light irradiation. Engagement of this approach allows for mild, efficient, and selective functionalization of organic molecules. The broader impacts of this project include providing new and effective routes into building block molecules of importance in chemical biology and materials science. Moreover, this research has the potential to significantly reduce the cost of chemical reagents needed, and thus have a favorable impact on process efficiency and economy. In addition, Dr. Gevorgyan is actively engaging in outreach activities for recruiting undergraduate students into research, including members of groups that are currently underrepresented in science. Student involvement in research at UT-Dallas is projected to provide a forum for the expression and cultivation of student talent and creativity and enhance their career possibilities.In this project, Professor Gevorgyan’s team is developing new mild transition metal-free methods for generation of aryl-, vinyl-, alkyl- and heteroatom-centered radicals to unlock their potential in modern organic synthesis. The approach under development relies on single electron transfer (SET) reduction of electrophilic intermediates with nucleophilic reagents. This can be accomplished under mildly thermal or visible light-induced conditions. The initially forming radicals may undergo atom transfer (AT) or hydrogen atom transfer (HAT) to generate a transposed radical, which then is involved in further synthetic transformations, including aliphatic C(sp3)−H bond functionalization, desaturation, or cascade cyclization reactions. The factors favoring efficient SET, AT, and HAT processes are under investigation. These methods, if fully developed, would not only deepen our understanding of electron-transfer chemistry for generation of reactive intermediates, but would also substantially broaden the arsenal of tools available for synthetic and medicinal chemists for synthesis and late stage modification of complex molecules.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.

凭借该奖项，美国国家科学基金会化学部的化学合成项目正在支持 Gevorgyan 教授的研究。 他的研究团队正在开发新方法，将丰富且廉价的原料转化为增值产品。有机分子中大量存在的碳氢键是有用的阐述的目标。然而，碳氢键的高强度使其不易断裂，因此可能需要强制条件，例如高反应温度或使用贵重和稀有过渡金属。这种化学反应可能还需要使用高度不稳定的试剂，这会引起安全问题。 Gevorgyan 教授的团队正在研究非常温和且安全的无过渡金属方法，用于在可见光照射下从简单且稳定的前体生成和操纵各种活性物质。这种方法的参与可以实现有机分子的温和、高效和选择性功能化。该项目的更广泛影响包括为化学生物学和材料科学中重要的构建模块分子提供新的有效途径。此外，这项研究有可能显着降低所需化学试剂的成本，从而对工艺效率和经济性产生有利影响。此外，Gevorgyan 博士还积极参与招募本科生参与研究的外展活动，其中包括目前在科学领域代表性不足的群体的成员。 学生参与德克萨斯大学达拉斯分校的研究预计将为学生的才华和创造力的表达和培养提供一个论坛，并增强他们的职业可能性。在这个项目中，Gevorgyan 教授的团队正在开发新的温和无过渡金属方法，用于生成以芳基、乙烯基、烷基和杂原子为中心的自由基，以释放其在现代有机合成中的潜力。正在开发的方法依赖于亲核试剂对亲电子中间体的单电子转移（SET）还原。这可以在温和的热或可见光诱导的条件下完成。最初形成的自由基可能会经历原子转移（AT）或氢原子转移（HAT）以产生转置自由基，然后该自由基参与进一步的合成转化，包括脂肪族C(sp3)-H键功能化、去饱和或级联环化反应。有利于高效 SET、AT 和 HAT 流程的因素正在研究中。这些方法如果得到充分开发，不仅将加深我们对用于生成反应中间体的电子转移化学的理解，而且还将大大拓宽合成和药物化学家可用于复杂分子的合成和后期修饰的工具库。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力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

Recent Advances in Dual Triplet Ketone/Transition-Metal Catalysis

• DOI: 10.1055/s-0042-1751444
• 发表时间: 2023-01
• 期刊: Synlett
• 影响因子: 2
• 作者: Valeriia Iziumchenko;V. Gevorgyan