Organocatalytic Enantioselective Sigmatropic Rearrangements to Probe Divergent Reactivity of Reactive Intermediates

有机催化对映选择性齐向重排以探测反应中间体的不同反应性

• 批准号: 1955044
• 负责人: Stacey Brenner-Moyer
• 金额: $ 46.5万
• 依托单位: Rutgers University Newark
• 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: 2020-07-15 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955044&HistoricalAwards=false
• 关键词: Organocatalytic; Enantioselective; Sigmatropic; Rearrangements; Probe

Divergent reactivity is a phenomenon that occurs when reacting molecules can follow two competing reaction pathways, each leading to different products. This reactivity can be both an advantage and disadvantage in the synthesis of organic molecules. If the factors dictating the reaction pathways are well understood, divergent reactivity can be deliberately manipulated and harnessed to advantage. When this fundamental understanding is lacking, however, this dual reactivity diminishes synthetic utility. In this project, with the support from the Chemical Catalysis Program of the Chemistry Division, Professor Brenner-Moyer of Rutgers University-Newark is investigating the influence of catalysts on divergent reactivity. Catalysts are substances that increase the rates of chemical reactions but are themselves not consumed, and are of enormous importance in fundamental and industrial chemistry. This knowledge gained from this research ultimately enables improved control of reaction outcomes, permitting direct access to useful chemicals. Professor Brenner-Moyer and her group are especially interested in new strategies to synthesize alkaloids, which are a broad class of naturally occurring compounds that exhibit a range of biological activities. Professor Brenner-Moyer is also coordinating a peer-mentoring program for academically at-risk, first-year female students interested in the sciences, with the goal of increasing their retention as STEM (science, technology, engineering, mathematics) majors. In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Brenner-Moyer of the Department of Chemistry at Rutgers University-Newark is investigating catalyst control in reactions of dienamine and ammonium ylide intermediates through the lens of new reaction development. These investigations entail a combination of synthetic studies, including the design and synthesis of new reaction catalysts, and synthetic mechanistic studies. Findings of these studies improve catalysts used in divergent reactions; this is a crucial step in harnessing their enormous synthetic potential for advanced manufacturing. Specifically, attaining generally accepted models for catalyst control of dienamine and ammonium ylide intermediates enables access to valuable enantiopure, remotely functionalized aldehyde synthons and complex alkaloid structures, respectively. Concurrent with these research activities, Professor Brenner-Moyer also coordinates a peer-mentoring program for first-year female Louis Stokes Alliances for Minority Participation (LSAMP) and Educational Opportunity Fund (EOF) students designed to increase their retention as STEM majors.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.

发散反应性是当反应分子遵循两条竞争的反应途径（每条途径产生不同的产物）时发生的现象。这种反应性在有机分子的合成中既是优点也是缺点。如果决定反应途径的因素得到很好的理解，就可以有意地操纵和利用不同的反应性。然而，当缺乏这种基本理解时，这种双重反应性就会降低合成效用。在该项目中，在化学系化学催化项目的支持下，罗格斯大学纽瓦克分校的Brenner-Moyer教授正在研究催化剂对不同反应性的影响。催化剂是提高化学反应速率但其本身不被消耗的物质，在基础化学和工业化学中具有极其重要的作用。从这项研究中获得的知识最终能够改善对反应结果的控制，从而允许直接获取有用的化学品。 Brenner-Moyer 教授和她的团队对合成生物碱的新策略特别感兴趣，生物碱是一大类天然存在的化合物，具有一系列生物活性。 Brenner-Moyer 教授还在协调一项针对学术上有风险、对科学感兴趣的一年级女学生的同伴辅导计划，目标是提高她们在 STEM（科学、技术、工程、数学）专业的保留率。在这个由化学部化学催化项目资助的项目中，罗格斯大学纽瓦克分校化学系的 Brenner-Moyer 教授正在通过新反应发展的视角研究二烯胺和铵叶立德中间体反应中的催化剂控制。这些研究需要综合研究的结合，包括新反应催化剂的设计和合成以及合成机理研究。这些研究的结果改进了不同反应中使用的催化剂；这是利用其巨大合成潜力进行先进制造的关键一步。具体来说，获得普遍接受的二烯胺和铵叶立德中间体催化剂控制模型可以分别获得有价值的对映体纯、远程功能化的醛合成子和复杂的生物碱结构。在开展这些研究活动的同时，Brenner-Moyer 教授还为 Louis Stokes 少数族裔参与联盟 (LSAMP) 和教育机会基金 (EOF) 女一年级学生协调一项同伴辅导计划，旨在提高她们在 STEM 专业的保留率。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。