CAREER: SusChEM: Anomeric Activation Strategy for Catalytic, Ketyl Radical Reactivity

职业：SusChEM：催化、羰基自由基反应的异头激活策略

基本信息

批准号：
1654656
负责人：
David Nagib
金额：
$ 70万
依托单位：
Ohio State University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2017
资助国家：
美国
起止时间：
2017-07-01 至 2022-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1654656&HistoricalAwards=false
关键词：
CAREER SusChEM Anomeric Activation Strategy

项目摘要

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor David Nagib of the Department of Chemistry and Biochemistry at The Ohio State University. Professor Nagib is developing new areas of synthetic chemistry that complement the methods currently used to synthesize complex organic molecules with applications ranging from pharmaceuticals and agrochemicals to biofuels and new functional materials. The goal of this research is to develop environmentally friendly catalysts using earth-abundant metals that can more easily generate a particular type of reactive intermediate known as a free radical, while also harnessing their reactivity in a controlled and selective fashion. An integral part of this program is the inclusion of underrepresented groups in this research, including high school, college, and graduate students. Professor Nagib's research team seeks to simultaneously increase interest, participation, retention, and literacy in Science, Technology, Engineering and Mathematics (STEM) fields by (a) offering hands-on research experience via a summer internship program for a diverse group of high-school and undergraduate students; (b) sharing interactive science demonstrations with local K-12 students; (c) creating informative and accessible visual media for the general public; and (d) sharing knowledge and research about radical chemistry through social media, online forums, and community outreach activities.This integrated research, education, and outreach program is focused on enabling a complementary class of polarity-reversed, radical reactivity for carbonyls. The transformation of this ubiquitous synthetic handle from its native, electrophilic nature to an umpolung, nucleophilic ketyl radical is achieved through an anomeric activation strategy. This approach relies on in situ conversion of carbonyls to alpha-oxy intermediates, which are better suited for radical generation using mild catalysts derived from earth-abundant metals. This dual-catalytic strategy for generation of ketyl radicals is superior to current approaches that rely on strong, stoichiometric reductants to overcome the high reduction potential for single electron transfer (SET) to carbonyls. This technology has broad applicability for the development of sustainable tools for streamlining the synthesis of complex medicines and materials. Integrated outreach activities involving multimedia demonstration of the vital role of free radicals and organic chemistry in daily life is also a key aspect of this funded project.

化学系化学合成项目支持俄亥俄州立大学化学与生物化学系 David Nagib 教授的项目。纳吉布教授正在开发合成化学的新领域，以补充目前用于合成复杂有机分子的方法，其应用范围从制药和农用化学品到生物燃料和新功能材料。这项研究的目标是使用地球上储量丰富的金属开发环境友好型催化剂，这些金属可以更容易地生成一种称为自由基的特定类型的反应中间体，同时还以受控和选择性的方式利用其反应性。该计划的一个组成部分是将代表性不足的群体纳入这项研究，包括高中生、大学学生和研究生。 Nagib 教授的研究团队力求通过以下方式同时提高对科学、技术、工程和数学 (STEM) 领域的兴趣、参与度、记忆力和素养：(a) 通过暑期实习计划为不同群体的高水平学生提供实践研究经验。在校学生和本科生； (b) 与当地 K-12 学生分享互动科学演示； (c) 为公众创建信息丰富且易于使用的视觉媒体； (d) 通过社交媒体、在线论坛和社区外展活动分享有关自由基化学的知识和研究。这一综合研究、教育和外展计划的重点是实现羰基的极性反转自由基反应性的互补类。这种普遍存在的合成手柄从其天然的亲电性质转变为反极性亲核羰基自由基是通过异头活化策略实现的。这种方法依赖于羰基到α-氧基中间体的原位转化，这种中间体更适合使用源自地球丰富的金属的温和催化剂产生自由基。这种产生羰基自由基的双催化策略优于目前依赖强化学计量还原剂来克服单电子转移（SET）到羰基的高还原电位的方法。该技术对于开发简化复杂药物和材料合成的可持续工具具有广泛的适用性。综合外展活动涉及多媒体演示自由基和有机化学在日常生活中的重要作用也是该资助项目的一个关键方面。