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

化学部门的化学合成项目支持俄亥俄州立大学化学和生物化学系的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的功能材料。这项研究的目标是利用地球上丰富的金属来开发环境友好型催化剂，这种催化剂可以更容易地产生一种被称为自由基的特殊类型的反应中间体，同时也可以以受控和选择性的方式利用它们的反应性。这个项目的一个组成部分是在这项研究中纳入代表性不足的群体，包括高中生、大学生和研究生。Nagib教授的研究团队寻求同时提高对科学、技术、工程和数学（STEM）领域的兴趣、参与、保留和素养，方法是(a)通过暑期实习计划为不同群体的高中和本科生提供实践研究经验；(b)与本地K-12学生分享互动科学示范；(c)为一般公众创造信息丰富和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。这个综合研究，教育和推广计划的重点是使一个互补类极性反转，羰基自由基反应性。这种无处不在的合成柄从其原生的亲电性质转变为非极性的亲核基自由基，是通过一种球端活化策略实现的。这种方法依赖于羰基到α -氧中间体的原位转化，α -氧中间体更适合于使用从地球上丰富的金属中提取的温和催化剂产生自由基。这种生成基自由基的双催化策略优于目前依赖于强化学计量还原剂的方法，以克服单电子转移（SET）到羰基的高还原潜力。这项技术对于开发可持续的工具以简化复杂药物和材料的合成具有广泛的适用性。综合推广活动包括多媒体展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重要方面。

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.