SusChEM: Advancing Organoelement Synthesis through alpha Elimination and Hydrophosphination Catalysis

化学部的化学催化计划支持罗里·沃特曼教授的项目。沃特曼教授是佛蒙特州大学化学系的教员。这项提议的目标是发现和理解形成磷-碳和硅-碳键的催化反应。实现这一目标的核心是利用丰富的金属作为催化剂，以提供各种试剂与磷-氢和硅-氢键的不同化学反应活性。将探索两个具体的反应：α消除和氢磷化。α消除是一种罕见的相对较新的反应，有可能促进复杂分子结构的合成。这些结构在材料科学、催化和生物医学中都有应用。氢磷化是一种公认的转变，但仍然存在问题和限制。例如，克服这些挑战使这种反应可以在药物合成中得到更广泛的应用。提高对这两种反应的理解将推动数十亿美元的催化领域的发展。沃特曼教授已经能够成功地招收在科学界代表性较低的学生，为高中生提供研究经验，并与K-12学生进行教育拓展，这些做法将在该项目中继续下去。该提案探索了两种独特的催化剂，以了解和改进E-碳(C)(E=磷或硅)键的催化制备，认识到在不饱和底物存在的情况下，丰富而廉价的金属可以在E-氢(H)键激活时产生不同的反应活性。通过一系列可检验的假设，寻找了一套经过验证的阿尔法消除催化设计特征。这种反应可能通过催化E-C键的形成来高效地合成含磷和硅的分子，这是一个关键的驱动因素。该小组以前的发现表明，这种新的反应性是可能的，这一领域的努力寻求提高对M-E成键和反应化学的理解。通过氢化反应发现新的高效合成手性磷配体的努力为解决这些根本问题提供了一个平台，并扩大了对这一关键的P-C键形成反应的理解和应用。除了材料科学、能源和生物医学等领域的这些反应的好处外，该推广计划还包括为高中生提供直接的研究经验，以支持项目目标。

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.