CAREER: Expanding the Toolbox for Olefin Functionalization and Difunctionalization Reactions

职业生涯：扩展烯烃官能化和双官能化反应的工具箱

• 批准号: 2047725
• 负责人: Michael Young
• 金额: $ 64.86万
• 依托单位: University of Toledo
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2047725&HistoricalAwards=false
• 关键词: CAREER; Expanding; Toolbox; Olefin; Functionalization

With the support of the Chemical Synthesis Program in the Division of Chemistry, Michael Young of The University of Toledo is developing new ways to install new molecular fragments at both carbon atoms of an alkene by using reaction additives to control the regiochemistry. Alkenes are common feedstock chemicals that are obtained from both petrochemical and bio-based sources. Despite the many existing strategies that have been studied for selectively converting alkene building blocks into value-added products, there are still challenges associated with the formation of product mixtures and the need for wasteful intermediate synthetical steps. Dr. Young and his research team are working to control the reactions of alkenes with simple and abundant reaction additives such as carbon dioxide. These studies have the potential to permit for more efficient syntheses of valuable chemical building blocks for new pharmaceuticals, fine chemicals, and next generation materials. Dr. Young will also introduce the practice of solvent recycling to research students and into teaching labs to emphasize the importance of sustainability. In addition, online short courses on green chemistry principles are also being developed for students and the local chemical industry workforce.Directing groups have played an essential role in advancing the field of C-H functionalization and the development of transient directing groups continues to improve the synthetic efficiency of this important strategy for achieving selective reactivity. Dr. Michael Young and his students are developing ways to use transient directing group tools for internal olefin functionalization strategies. Specifically, the regioselective arylation of free amine-tethered alkenes with aryl halides is being investigated by changing reactions conditions. This approach is designed to both improve the selectivity of internal alkene arylation reactions and facilitate product diversification. In addition, 1,2-difunctionalization reactions of activated alkenes will be studied to install C-C and C-O/C-N bonds in the same step. Mechanistic studies are planned to guide optimization and synthetic application of this new chemistry. These activities are expected to provide new approaches to the rapid diversification of amine-containing compounds, which is beneficial for developing compound libraries to support the pharmaceutical and agrochemical industries. These activities will also provide an excellent training ground in synthetic and organometallic chemistry for a diverse group of graduate, undergraduate, and high school students, as well as a postdoctoral researcher.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，托莱多大学的 Michael Young 正在开发新方法，通过使用反应添加剂来控制区域化学，在烯烃的两个碳原子上安装新的分子片段。烯烃是常见的化学原料，可从石化和生物来源获得。尽管已经研究了许多现有策略来选择性地将烯烃结构单元转化为增值产品，但仍然存在与产物混合物的形成和需要浪费的中间合成步骤相关的挑战。 Young博士和他的研究团队正在致力于用简单而丰富的反应添加剂（例如二氧化碳）来控制烯烃的反应。这些研究有可能更有效地合成新药物、精细化学品和下一代材料的有价值的化学结构单元。杨博士还将向研究生和教学实验室介绍溶剂回收的实践，以强调可持续性的重要性。此外，还为学生和当地化工行业人员开发了有关绿色化学原理的在线短期课程。导向基团在推进C-H官能化领域发挥了重要作用，瞬态导向基团的发展不断提高合成效率这一实现选择性反应的重要策略。 Michael Young 博士和他的学生正在开发使用瞬态导向基团工具进行内烯烃官能化策略的方法。具体来说，正在通过改变反应条件来研究游离胺系烯烃与芳基卤化物的区域选择性芳基化。该方法旨在提高内部烯烃芳基化反应的选择性并促进产品多样化。此外，还将研究活化烯烃的1,2-双官能化反应，以在同一步骤中安装C-C和C-O/C-N键。计划进行机理研究来指导这种新化学物质的优化和合成应用。这些活动预计将为含胺化合物的快速多样化提供新方法，这有利于开发化合物库以支持制药和农化行业。这些活动还将为不同群体的研究生、本科生和高中生以及博士后研究员提供合成和有机金属化学方面的良好培训基地。该奖项反映了 NSF 的法定使命，并通过评估被认为值得支持利用基金会的智力优势和更广泛的影响审查标准。

项目成果

Amine-directed Mizoroki–Heck arylation of free allylamines

胺引导的游离烯丙胺的 Mizoroki–Heck 芳基化

• DOI: 10.1039/d2qo00041e
• 发表时间: 2022
• 期刊: Organic Chemistry Frontiers
• 影响因子: 5.4
• 作者: Landge, Vinod G.;Bonds, Audrey L.;Mncwango, Thandazile A.;Mather, Carolina B.;Saleh, Yasaman;Fields, Hunter L.;Lee, Frank;Young, Michael C.
• 通讯作者: Young, Michael C.

Oxidative Mizoroki–Heck reaction of unprotected cinnamylamines at ambient temperature under air

未保护的肉桂胺在环境温度下空气中的氧化 MizorokiâHeck 反应

• DOI: 10.1039/d3qo00778b
• 发表时间: 2023
• 期刊: Organic Chemistry Frontiers
• 影响因子: 5.4
• 作者: Farinde, Olutayo N.;Satheesh, Vanaparthi;Shrestha, Kendra K.;Rhinehalt, Carmen R.;Landge, Vinod G.;Young, Michael C.
• 通讯作者: Young, Michael C.