Formation of Organic Products by Oxidation of Metal Carbynes

这个无机、生物无机和有机金属化学项目的奖项支持佛罗里达大学化学系的Lisa mcelee - white博士关于在有机合成中使用金属碳炔的研究。将开发七元和八元金属环、环丁酮、熔融乙烯基环丙烷、呋喃、低聚物和其他产品的新路线。钼和钨碳炔在光解过程中形成自由基阳离子和碳烯中间体。经过碳炔配体的重排和损失，可以生成多种有机产物。例如，含有系链烯烃和二烯的碳炔取代基配合物可以通过分子内烯反应、环丙烷化、复分解或4+2环加成捕获中间体。通过自由基阳离子攻击不饱和物质形成的碳-碳键也可以被利用，分子内捕获也可以产生环化产物。金属与碳通过三键结合的有机金属化合物称为碳炔。虽然人们对这些化合物的反应了解很多，但它们还没有被用于有机合成。在本研究中，将使用这种方法制备各种各样的环状有机化合物，这可能为许多复杂的有机结构提供简单的途径。

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.