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

该奖项全部或部分根据2021年美国救援计划法案（公法117-2）资助。 在这个项目中，由数学和物理科学理事会资助，并设在化学部，教授Allegra Liberman-Martin和本科生在查普曼大学将开发无金属催化剂，用于小有机分子和聚合物的可持续制备。许多现有的催化剂使用昂贵、稀有或有毒的金属，因此需要开发基于地球丰富元素的高效和耐用的催化剂。利伯曼-马丁教授和她的学生将研究具有中性、富电子碳中心的催化剂。这项研究将提高对富电子碳催化剂反应途径的理解，同时还提供涉及酯底物的新催化方法，这些酯底物存在于生物质和植物油中。Liberman-Martin教授的扩大参与计划为查普曼大学的STEM转学生创造了一个定向计划，一个学期的研究机会和每月的研讨会系列。Liberman-Martin教授和查普曼大学的本科生将研究正膦和磷叶立德的有机催化反应性。这两种催化剂类别的特点是富电子碳中心两侧有一个或两个磷取代基。尽管正膦烷已被研究用作支持无机配合物的配体，并且磷叶立德通常用作有机合成的试剂，但它们的催化行为仍然相对未被探索。本项目研究酯衍生化过程中的催化作用，目标是酯还原和开环聚合反应。该项目的发现有可能拓宽化学家可用的有机催化方法，并提高对正膦结构和反应性的基本理解。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.