Mechanisms and Applications of Rhenium-Mediated O Atom Transfer

铼介导的O原子转移机制及应用

• 批准号: 0078505
• 负责人: Kevin Gable
• 金额: $ 28.8万
• 依托单位: Oregon State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-07-15 至 2004-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0078505&HistoricalAwards=false
• 关键词: Mechanisms; Applications; Rhenium; Mediated; Atom

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.

有机和大分子化学计划通过这一更新奖支持俄勒冈州科瓦利斯州俄勒冈州立大学化学系凯文·p·盖博博士的工作。该研究将扩展对二酸盐环还原的研究，以研究一种新的环氧化物脱氧机制，以确定环氧化物是进行同步还是异步键裂解。将开启对铼介导的o原子转移有用应用的新探索。氧选择性转移到有机分子中是一类重要的有机反应。一种方法是从低价过渡金属络合物中裂解O2形成活性M=O单元。然后烯烃反应生成环氧化物或二酸盐配合物，分别形成一个或两个新的C-O键。这里所做的大部分工作，涉及到二酸氧(V)配合物的环还原，涉及到微观的逆转。从热力学上讲，氧原子向磷（III）的转移比向碳的转移更有利。调整LReO3中配体的空间性质，可以通过选择性氧化其中一种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在他的研究中包含了大量的本科生。