LEAPS-MPS: Development of Carbodiphosphorane Catalysts for Organic and Polymer Synthesis

Chapman University, Orange CA

Investigators

Abstract

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2). In this project, funded by the Mathematical and Physical Sciences Directorate and housed in the Chemistry Division, Professor Allegra Liberman-Martin and undergraduate students at Chapman University will develop metal-free catalysts for the sustainable preparation of small organic molecules and polymers. Many current catalysts use expensive, rare, or toxic metals, creating an ongoing need to develop efficient and robust catalysts based on earth-abundant elements. The Prof. Liberman-Martin and her students will study catalysts that feature neutral, electron-rich carbon centers. This investigation will improve understanding of reaction pathways for electron-rich carbon catalysts while also providing new catalytic methods involving ester substrates, which are found in biomass and plant-based oils. Prof. Liberman-Martin’s broadening participation plan creates an orientation program, one-semester research opportunity, and monthly workshop series for STEM transfer students at Chapman University. Prof. Liberman-Martin and Chapman University undergraduates will study the organocatalytic reactivity of carbodiphosphoranes and phosphorus ylides. Both catalyst categories feature an electron-rich carbon center flanked by one or two phosphorus substituents. Although carbodiphosphoranes have been investigated as ligands to support inorganic complexes and phosphorus ylides are commonly used as reagents for organic synthesis, their catalytic behavior remains relatively unexplored. This project studies catalysis in the context of ester derivatization and targets both ester reduction and ring-opening polymerization reactions. Discoveries from this project have the potential to broaden the organocatalytic methods available to chemists and improve the fundamental understanding of carbodiphosphorane structure and reactivity. 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.