SusChEM: Mechanism-based development of new nickel-catalyzed stereospecific ring-contraction and reductive coupling reactions

加州大学欧文分校的Elizabeth Jarvo教授在化学系化学催化计划的资助下，正在开发用于立体选择性合成的地球丰富的镍催化剂。 这项研究的更广泛的影响包括从地球丰富的元素中开发容易获得的催化剂，减少美国对贵金属催化剂的依赖，并提高可持续性。 研究生接受有机和有机金属实验室技术和机械研究的培训。 针对妇女和少数民族研究生和教师的辅导和职业发展讲习班被纳入该计划。外展工作涉及代表性不足的群体，并开发技能集，以保留在广泛的年龄范围内，从中学生到研究生，博士后研究员和初级教师。 通过与当地学校合作，服务不足的中学生参与加州大学欧文分校的STEM研究环境和机会。 由Jarvo教授共同创立的LEAPS外展计划为服务不足和代表性不足的中学生提供了一天的大学体验，包括将他们的课堂作业与化学和物理学的前沿研究联系起来的实验。 该项目的重点是完善有机镍络合物的双电子反应的机理理解，这是开发用于一系列转化的镍催化剂的关键一步。 除了为贵重钯催化剂提供更可持续的替代品之外，镍催化剂还提供独特的反应性模式和优点，特别是在通常缓慢的底物的反应中以及用于合成新的三级立体中心。活性催化剂的身份正在使用动力学和结构分析，包括NMR和EPR光谱和X射线晶体学来确定。 新的反应性流形，包括还原环收缩的卤代四氢呋喃，正在开发挑战的机制假设，并提供实用的合成取代环丙烷，药效团在药物化学。

AbstractIn this project funded by the Chemical Catalysis program of the Chemistry Division, Professor Elizabeth Jarvo of the University of California, Irvine is developing earth abundant nickel catalysts for stereoselective synthesis. The broader impacts of this research include development of readily available catalysts from earth abundant elements, reducing the US dependence on precious metal catalysts, and increasing sustainability. Graduate students are trained in organic and organometallic laboratory techniques and in mechanistic investigation. Mentoring and career-development workshops that target women and minority graduate students and faculty are integrated into the program. Outreach efforts engage underrepresented groups and develop skills sets for retention across a wide range of ages, from middle school students to graduate students, postdoctoral fellows, and junior faculty. Through partnering with local schools, underserved middle school students participate in STEM research environment and opportunities at UC Irvine. The LEAPS outreach program co-founded by Professor Jarvo provides underserved and underrepresented middle school students with a day at college experience, including hands on experiments that connect their classwork with cutting-edge research in chemistry and physics. This project focuses on refining the mechanistic understanding of two-electron reactions of organonickel complexes, a critical step forward in the development of nickel catalysts for a range of transformations. In addition to providing a more sustainable alternative for precious palladium catalysts, nickel catalysts provide unique reactivity patterns and advantages, particularly in reactions of typically sluggish substrates and for the synthesis of new tertiary stereogenic centers. The identities of active catalysts are being defined using kinetic and structural analysis, including NMR and EPR spectroscopy and X-ray crystallography. New reactivity manifolds, including reductive ring-contractions of halotetrahydrofurans, are being developed to challenge the mechanistic hypotheses and provide practical syntheses of substituted cyclopropanes, pharmacophores in medicinal chemistry.