Acceptor-Acceptor Carbenoids in Selective Insertions and Cyclizations

利用这一奖项，化学合成项目将支持犹他大学的Jon Rainier教授研究重氮膦酸乙烯基和重氮乙烯基膦酸乙烯基转化为受体-受体Rh碳烯，并将碳烯与醇、胺和硫醇进行插入反应。这项工作将包括对具有独特性质的新型底物和反应的研究。许多这些物质和反应的灵感来自于自然和非自然发生的小分子，这些小分子已被证明具有生物活性。因此，这些研究将产生在化学和制药工业中具有潜在高影响的新材料。Rainier教授将把该项目的研究和教育内容整合到犹他大学的教学课程中，以及他与美国化学学会学生分会的工作中。通过将研究项目纳入本科课程，雷尼尔教授希望激励下一代科学家从事化学事业。通过他与学生联盟的参与，雷尼尔教授通过动手实验，研讨会和示范接触了许多中小学生，试图促进好奇心和STEM教育。在本研究中，将发展涉及受体-受体乙烯基羰基的新方法，用于合成含膦酸盐材料和小分子。为实现这些目标而进行的工作是独一无二的，因为它将提供对含有碳烯的膦酸盐性质的更好的基本理解，并且具有实用价值。Rainier教授和他的团队将探索电子和空间扰动对金属碳烯和底物对重氮膦酸乙烯基插入化学的影响。在这项工作的过程中，将产生一系列含磷酸盐的小分子。初步证据表明，这些产物可能具有作为具有生物活性的小分子和作为功能化铁纳米粒子的配体的潜力，它们本身也可能应用于生物系统中小分子和基因的递送。

With this award, the Chemical Synthesis Program is supporting Professor Jon Rainier at the University of Utah to study the conversion of vinyl diazophosphonates and diazo vinylphosphonates into acceptor-acceptor Rh carbenes and use the carbenes in insertion reactions with alcohols, amines, and thiols. Included in this work will be the examination of novel substrates and reactions having unique properties. The inspiration for many of these substances and reactions came from both naturally and non-naturally occurring small molecules that have been shown to be biologically active. As a consequence, these studies will generate new materials of potentially high impact in the chemical and pharmaceutical industry. Professor Rainier will integrate the research and educational components of this project into the teaching curriculum at the University of Utah as well as into his work with the American Chemical Society Student Affiliates. By bringing research projects into the undergraduate curriculum, Professor Rainier hopes to inspire the next generation of scientists to careers in chemistry. Through his involvement with the Student Affiliates, Professor Rainier has reached out to many elementary and middle school students through hands on experiments, workshops and demonstrations in an attempt to promote curiosity and STEM education. In this research, new methods involving acceptor-acceptor vinyl carbenes will be developed for the synthesis of phosphonate containing materials and small molecules. The work that will be carried out in pursuit of these goals is unique in that it will both provide a better fundamental understanding of the properties of phosphonate containing carbenes and in that it will have practical value. Professor Rainier and his group will explore the effect of electronic and steric perturbations on metal carbenes and substrates on the insertion chemistry of vinyl diazophosphonates. Over the course of this work, a range of phosphonate-containing small molecules will be generated. Preliminary evidence suggests that these products may have potential as bioactive small molecules and as ligands for functionalized iron nanoparticles, themselves with possible application in the delivery of small molecules and genes in biological systems.