SusChEM: Advancing Organoelement Synthesis through alpha Elimination and Hydrophosphination Catalysis

SusChEM：通过 α 消除和氢膦化催化推进有机元素合成

• 批准号: 1565658
• 负责人: Rory Waterman
• 金额: $ 42万
• 依托单位: University of Vermont & State Agricultural College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-05-01 至 2019-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1565658&HistoricalAwards=false
• 关键词: SusChEM; Advancing; Organoelement; Synthesis; through

The Chemical Catalysis Program of the Chemistry Division supports the project by Professor Rory Waterman. Professor Waterman is a faculty member in the Department of Chemistry at the University of Vermont. The objective of this proposal is to discover and understand catalytic reactions that form phosphorus-carbon and silicon-carbon bonds. Central to meeting that objective is utilizing abundant metals as catalysts to afford divergent chemical reactivity of phosphorus-hydrogen and silicon-hydrogen bonds with a variety of reagents. Two specific reactions will be explored: alpha elimination and hydrophosphination. Alpha elimination is a rare and relatively new reaction with the potential to facilitate the synthesis of complex molecular structures. These structures have applications in materials science, catalysis, and biomedicine. Hydrophosphination is a well-established transformation, but questions and limitations remain. Overcoming these challenges makes this reaction available for broader use in the synthesis of pharmaceuticals, for example. Improved understanding in both reactions would advance the multi-billion dollar field of catalysis. Professor Waterman has been able to successfully recruit students underrepresented in the sciences, provide research experiences for high school students, and engage in educational outreach with K-12 students, practices to be continued in this project. The proposal explores two unique kinds of catalysis to understand and improve the catalytic preparation of E- carbon (C) (E = phosphorus or silicon) bonds, recognizing that abundant and inexpensive metals can be enlisted to produce divergent reactivity upon E-hydrogen (H) bond activation in the presence of unsaturated substrates. Through a series of testable hypotheses, a validated set of design features for alpha elimination catalysis is sought. This reaction may result in the efficient synthesis of phosphorus- and silicon-containing molecules via catalytic E-C bond formation is a key driver. Prior discoveries in this group demonstrate that such new reactivity is possible, and efforts in this area seek to improve understanding of M-E bonding and reaction chemistry. Efforts to discover new and highly efficient syntheses of chiral-at-phosphorus ligands though hydrophosphination provide a platform to address those fundamental issues and broaden the understanding and utility of this key P-C bond forming reaction. Beyond the benefit of these reactions to fields such as materials science, energy, and biomedicine, the outreach program includes direct research experiences for high school students in support of project goals.

化学系的化学催化计划支持Rory Waterman教授的项目。沃特曼教授是佛蒙特大学化学系的教员。该计划的目标是发现和理解形成磷-碳和硅-碳键的催化反应。实现该目标的核心是利用丰富的金属作为催化剂，以提供磷-氢键和硅-氢键与各种试剂的不同化学反应性。将探讨两个具体的反应：α消除和氢化膦化。α消除是一种罕见且相对较新的反应，具有促进复杂分子结构合成的潜力。这些结构在材料科学、催化和生物医学中有应用。氢化磷化是一种成熟的转化方法，但仍存在问题和局限性。克服这些挑战使得该反应可用于更广泛的用途，例如药物合成。对这两种反应的进一步理解将推动价值数十亿美元的催化领域。教授沃特曼已经能够成功地招募学生在科学中代表性不足，为高中生提供研究经验，并从事教育推广与K-12学生，做法将继续在这个项目。 该提案探索了两种独特的催化剂，以理解和改进E-碳（C）（E =磷或硅）键的催化制备，认识到在不饱和底物存在下，丰富且廉价的金属可以被征用以在E-氢（H）键活化时产生不同的反应性。通过一系列可检验的假设，寻求α消除催化的一组经验证的设计特征。该反应可导致通过催化E-C键形成有效合成含磷和含硅分子，这是关键驱动因素。这个小组先前的发现证明了这种新的反应性是可能的，并且在这一领域的努力旨在提高对M-E键合和反应化学的理解。通过氢化膦化发现新的和高效的手性磷配体的合成的努力提供了一个平台，以解决这些基本问题，并拓宽了对这一关键的P-C键形成反应的理解和应用。除了这些反应对材料科学，能源和生物医学等领域的好处外，外展计划还包括高中生的直接研究经验，以支持项目目标。