Mechanisms and Applications of Rhenium-Mediated O Atom Transfer

通过这个续展奖项，有机和高分子化学项目支持俄勒冈州科瓦利斯市俄勒冈州立大学化学系的Kevin P.Gable博士的工作。这项研究将扩展二酸根环回反应的研究，以研究一种新的环氧化物的脱氧机理，以确定环氧化物是经历同步还是异步键断裂。Re介导的氧原子转移是一大类重要的有机反应，它将开启一种新的应用领域。一种方法是从低价过渡金属络合物中裂解O2以形成活性M=O单元。然后，烯烃反应可以生成环氧化物或二元醇配合物，其中分别形成一个或两个新的C-O键。这里所做的许多工作，包括氧-锗(V)二酸络合物的环反转，都涉及到微观的反转。氧原子转移到磷(III)比转移到碳更有利的热力学。通过调整配体在LREO_3中的空间性质，可以通过选择性地氧化其中一个对映体来分离手性膦的外消旋混合物。该项目投资的一个吸引人的特点是，PI在他的研究中包括了大量的本科生。

With this renewal award the Organic and Macromolecular Chemistry Program supports the work of Dr. Kevin P. Gable of the Department of Chemistry at Oregon State University in Corvallis, Oregon. The research will extend investigations of diolate cycloreversion to study the mechanism of a new epoxide deoxygenation, to determine whether the epoxide undergoes synchronous or asynchronous bond cleavage. A new exploration of useful applications of rhenium-mediated O-atom transfer will be initiated.Selective transfer of oxygen into organic molecules is a large and important class of organic reactions. One approach is to cleave O2 to form reactive M=O units from a low-valent transition metal complex. Reaction of olefins could then give epoxide or diolate complexes in which one or two new C-O bonds are formed, respectively. Much of the work done here, involving the cycloreversion of oxorhenium(V) diolate complexes, involves the microscopic reverse. Oxygen atom transfer to phosphorus(III) is more thermodynamically favorable than transfer to carbon. Tailoring the steric properties of the ligand in LReO3 should make it possible to separate racemic mixtures of chiral phosphines by selective oxidation of one of the enantiomers. An attractive feature of investment in the project is that the PI includes a large number of undergraduates in his research.