Mechanism-based development of new nickel-catalyzed stereospecific cross-electrophile coupling reactions of sulfonamides

通过这一奖项，化学系的化学合成计划支持了加州大学欧文分校化学系伊丽莎白·贾沃教授的研究。贾沃教授正在开发新的方法来制造用于农业、制药、聚合物和其他材料的含碳分子。制造这些分子的传统方法依赖于供应有限的贵金属，因此价格昂贵，有时很难获得。贾沃博士正试图用更富含稀土的镍基试剂来取代这些金属，这些试剂在环境上更具可持续性。随着对反应如何发生的关注，贾沃实验室对工业上重要的碳-碳键形成反应有了新的见解。该项目为研究生和本科生提供实践培训。贾沃教授还组织了职业发展研讨会，面向女性和代表性不足的教职员工和研究生。她为南加州大学的本科生共同组织了为期一天的研究研讨会，并参与了将加州大学欧文分校与附近服务不足的中学连接起来的外联项目。伊丽莎白·贾沃教授正在使用镍催化剂开发苯磺酰胺的立体特异性交叉偶联和交叉亲电偶联反应。这些新的催化方法使合成复杂的生物活性分子成为可能。例如，这项工作正在为环丙烷的合成确定立体选择性策略，环丙烷是药物化学中的一个特权部分。重要的是，机械实验阐明了控制有机镍络合物反应性的因素，使之有利于双电子反应而不是单电子反应，这是镍催化反应发展中的一个长期挑战。有机镍中间体的结构表征为关键催化中间体的氧化状态提供了实验证据，并有助于新催化剂的设计。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。

With this award, the Chemical Synthesis Program of the Division of Chemistry supports the research of Professor Elizabeth Jarvo in the Department of Chemistry of the University of California, Irvine. Professor Jarvo is developing new ways to make carbon-containing molecules used in agriculture, pharmaceuticals, polymers and other materials. Traditional methods of making these molecules rely on precious metals that are limited in supply and thus, expensive and sometimes hard to obtain. Dr. Jarvo is trying to replace those metals with more earth abundant nickel-based reagents that would be more environmentally sustainable. With a focus on how the reaction occurs, the Jarvo laboratory is gaining new insight into carbon-carbon bond forming reactions that are important industrially. This project provides hands-on training to graduate and undergraduate students. Professor Jarvo also organizes career-development workshops that target female and underrepresented faculty and graduate students. She co-organizes a day-long research symposium for Southern California undergraduate students and participates in outreach programs that connect the UC Irvine campus to nearby underserved middle schools.Professor Elizabeth Jarvo is developing stereospecific cross-coupling and cross-electrophile coupling reactions of benzylic sulfonamides using nickel catalysts. These new, catalytic methods enable the synthesis of complex biologically active molecules. For example, the work is defining stereoselective strategies for the synthesis of cyclopropanes, a privileged moiety in medicinal chemistry. Importantly, mechanistic experiments clarify the factors that govern reactivity of organonickel complexes to favor two-electron reactions versus single-electron reactions, a long-standing challenge in development of nickel-catalyzed reactions. Structural characterization of organonickel intermediates provides experimental evidence for the oxidation state of key catalytic intermediates and facilitates the design of new catalysts.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.