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

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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.