CAREER: New Catalytic Reactions of Nitroxy Compounds

在这项由化学系化学合成计划资助的项目中，德克萨斯大学圣安东尼奥分校的奥列格·拉里奥诺夫教授正在开发能够控制含氮化合物的反应性和立体选择性的催化系统。特别是，这项工作试图为过渡金属催化剂与高活性亚硝基烯、N-氧化物和恶嗪的相互作用提供基本的见解，这些都是生物碱的有价值的前体，其中许多具有重要的药用性质。该教育计划包括为研究生和高级本科生开发一门以有机合成为重点的课程，以实施以过程为导向的引导性探究学习技术。此外，外联工作通过让当地K-12科学教师参与服务不足的人群的工作，在K-12教育中促进可持续化学的想法和原则。含氮化合物的化学以不同的化学性质和反应活性来区分。这种无与伦比的多样性对开发利用含氮化合物独特反应性的合成方法是一个挑战。特别是，区域和立体选择性的控制是这些化合物的一个长期存在的问题。本研究的重点是影响亚硝基烯、N-氧化物和恶嗪的环化反应和碳-碳键形成反应的区域和立体化学结果的基本因素。该项目中发现的催化反应预计将影响到邻近的几个研究领域，包括材料科学、生物有机化学和催化。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Oleg Larionov of The University of Texas at San Antonio is developing catalytic systems that can control the reactivity and stereoselectivity of nitroxy compounds. In particular, this work is seeking to provide fundamental insights into the interactions of transition-metal catalysts with highly reactive nitrosoalkenes, N-oxides and oxazines that are valuable precursors to alkaloids, many of which have important medicinal properties. The educational plan involves the development of a course focused on organic synthesis for graduate and advanced-level undergraduate students implementing process-oriented, guided-inquiry learning techniques. In addition, outreach efforts promote the ideas and principles of sustainable chemistry in the K-12 education by engaging local K-12 science teachers who are working with underserved populations. The chemistry of nitroxy compounds is distinguished by a diversity of chemical properties and reactivities. This unmatched diversity is a challenge for the development of synthetic methods exploiting unique reactivities of nitroxy compounds. In particular, control of regio- and stereoselectivity is a long-standing problem for these compounds. This study focuses on the fundamental factors that influence the regio- and stereochemical outcomes of cycloannulations and carbon-carbon bond-formation reactions of nitrosoalkenes, N-oxides, and oxazines. The catalytic reactions discovered in this project are expected to impact several adjacent research areas, including materials science, bioorganic chemistry and catalysis.