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.

化学部的化学催化计划由罗里·沃特曼（Rory Waterman）教授支持该项目。沃特曼教授是佛蒙特大学化学系的教职员工。该提案的目的是发现和理解形成磷碳和硅碳键的催化反应。达到该目标的核心是利用丰富的金属作为催化剂，可提供与多种试剂的磷氢和硅氢键的不同化学反应性。将探索两个特定的反应：消除α和水磷。消除α是一种罕见且相对较新的反应，具有促进复杂分子结构的合成的潜力。这些结构在材料科学，催化和生物医学中具有应用。水圈是一个公认的转变，但仍然存在问题和局限性。例如，克服这些挑战使得该反应可用于在制药合成中更广泛地使用。在这两种反应中的理解都提高了，将推动数十亿美元的催化领域。沃特曼教授已经能够成功地招募学生在科学领域的人数不足，为高中生提供研究经验，并与K-12学生进行教育宣传，并在该项目中继续进行实践。 该提案探讨了两种独特的催化类型，以理解和改善电子碳（C）（C）（e =磷或硅）键的催化制备，认识到可以征集丰富且廉价的金属在不饱和次次次生物的存在下，可以在E-Hydrogen（H）键激活的情况下产生发散的反应性。通过一系列可检验的假设，寻求一组经过验证的α消除催化设计特征。该反应可能导致通过催化E-C键的形成有效合成磷和含硅分子的反应是关键驱动力。该组中的先前发现表明，这种新的反应性是可能的，并且该领域的努力试图提高对M-E键和反应化学的理解。尽管水磷酸化，但努力发现手性配体配体的新的，高效的合成，为解决这些基本问题的平台提供了一个平台，并扩大了该关键P-C键形成反应的理解和实用性。除了这些对材料科学，能源和生物医学等领域的反应的好处外，外展计划还包括为支持项目目标的高中生的直接研究经验。