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.

在化学系化学合成计划的支持下，托莱多大学的迈克尔·杨正在开发新的方法，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。烯烃是一种常见的原料化学品，可从石化和生物来源获得。尽管已经研究了许多有选择性地将烯烃组分转化为增值产品的现有战略，但仍然存在与产品混合物的形成相关的挑战，以及需要浪费的中间合成步骤。杨博士和他的研究团队正在努力用二氧化碳等简单而丰富的反应添加剂来控制烯烃的反应。这些研究有可能更有效地合成用于新药物、精细化学品和下一代材料的有价值的化学构件。杨博士还将向研究学生和教学实验室介绍溶剂回收的实践，以强调可持续发展的重要性。此外，还为学生和当地化工工作者开发了关于绿色化学原理的在线短期课程。指导小组在推进C-H官能化领域发挥了重要作用，瞬时指导小组的发展继续提高了这一实现选择性反应的重要策略的合成效率。Michael Young博士和他的学生正在开发使用瞬时导向基团工具进行内部烯烃官能化策略的方法。具体地说，通过改变反应条件来研究游离胺系链烯与芳基卤化物的区域选择性芳基化反应。这种方法的目的是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，还将研究活性烯烃的1，2-二官能化反应，以便在同一步骤中建立C-C和C-O/C-N键。计划进行机理研究，以指导这种新化学的优化和综合应用。这些活动有望为含胺化合物的快速多样化提供新的途径，这有利于发展化合物库以支持制药和农用化学品工业。这些活动还将为不同的研究生、本科生和高中生以及博士后研究人员提供一个极好的合成和有机金属化学培训基础。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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

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.

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.