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可以遵循两个竞争反应途径时发生的现象，每个反应途径导致不同的产物。这种反应性在有机分子的合成中既可以是优点也可以是缺点。如果能很好地理解决定反应途径的因素，就可以有意地操纵和利用不同的反应性。然而，当缺乏这种基本的理解时，这种双重反应性就会降低合成的效用。在该项目中，在化学系化学催化计划的支持下，罗格斯大学纽瓦克分校的Brenner-Moyer教授正在研究催化剂对发散反应性的影响。催化剂是增加化学反应速率但本身不消耗的物质，在基础化学和工业化学中具有巨大的重要性。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，从而可以直接获得有用的化学品。Brenner-Moyer教授和她的团队对合成生物碱的新策略特别感兴趣，生物碱是一类广泛的天然化合物，具有一系列生物活性。Brenner-Moyer教授还为对科学感兴趣的学术风险，一年级女学生协调了一项同伴指导计划，目的是提高她们作为STEM（科学，技术，工程，数学）专业的保留率。在化学部化学催化计划资助的这个项目中，罗格斯大学纽瓦克分校化学系的Brenner-Moyer教授通过新反应开发的透镜研究了二烯胺和铵叶立德中间体反应中的催化剂控制。这些研究需要合成研究的组合，包括新反应催化剂的设计和合成，以及合成机理研究。这些研究的发现改进了用于发散反应的催化剂;这是利用其巨大的合成潜力进行先进制造的关键一步。具体地说，获得普遍接受的模型，用于催化剂控制的二烯胺和铵叶立德中间体，使访问有价值的对映体纯，远程官能化的醛类化合物和复杂的生物碱结构，分别。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（Educational Opportunity Fund）的一年级女学生协调了一项同伴指导计划，旨在提高她们作为STEM专业学生的保留率。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力审查标准进行评估，被认为值得支持。