Formation of Organic Products by Oxidation of Metal Carbynes

该奖项在无机，生物无机和有机化学计划支持的研究丽莎McElwee-White的化学系，佛罗里达大学，在有机合成中使用金属卡宾。 将开发七元和八元金属杂环、环丁酮、稠合乙烯基环丙烷、呋喃、低聚物和其他产物的新路线。 自由基阳离子和卡宾中间体形成在钼和钨卡宾的光解。 在碳炔配体的重排和损失之后，可能产生各种有机产物。 例如，含有碳炔取代基的络合物（其含有栓系烯烃和二烯）可以通过分子内烯反应、环丙烷化、复分解或4 + 2反应捕获中间体。 环加成 也可以利用自由基阳离子攻击不饱和物质形成碳-碳键，也可以利用分子内捕获产生环化产物。 其中金属通过三键与碳结合的有机化合物称为碳炔。 虽然对这些化合物的反应了解很多，但它们还没有用于有机合成。 在本研究中，各种各样的环状有机化合物将使用这种方法制备，这可能提供一个简单的路线，许多复杂的有机结构。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research by Dr. Lisa McElwee-White of the Chemistry Department, University of Florida, on the use of metal carbynes in organic synthesis. New routes to seven- and eight-membered metallacycles, cyclobutanones, fused vinylcyclopropanes, furans, oligomers, and other products will be developed. Radical cation and carbene intermediates are formed during photolysis of molybdenum and tungsten carbynes. After rearrangement and loss of the carbyne ligand, generation of a variety of organic products is possible. For example, complexes with carbyne substituents which contain tethered olefins and dienes can trap the intermediates by intramolecular ene reaction, cyclopropanation, metathesis or 4+2 cycloaddition. Carbon-carbon bond formation by attack of the radical cations on unsaturated species can also be exploited, as can intramolecular trapping to yield cyclized products. Organometallic compounds in which the metal is bound to carbon by a triple bond are called carbynes. Although much is known about the reactions of these compounds, they have not been used in organic synthesis. In this research, a wide variety of cyclic organic compounds will be prepared using this approach, which may offer a simple route to many complex organic structures.