Formation of Organic Products by Oxidation of Metal Carbynes

无机化学、生物无机化学和金属有机化学项目的这一奖项支持佛罗里达大学化学系的Lisa McElwee-White博士在有机合成中使用金属卡宾的研究。将开发合成七元和八元金属环、环丁酮、稠合乙烯基环丙烷、呋喃、齐聚物等产品的新路线。钼和钨的卡宾在光解过程中形成自由基阳离子和卡宾中间体。在卡宾配体重排和丢失后，有可能产生各种有机产品。例如，含有卡宾取代基的化合物可以通过分子内烯反应、环丙烷化、歧化或4+2环加成等方式捕获中间体。也可以利用自由基阳离子对不饱和物种的攻击形成碳-碳键，也可以利用分子内捕获来生成环化产物。金属与碳以三键结合的有机金属化合物称为卡宾。虽然人们对这些化合物的反应知道很多，但它们还没有被用于有机合成。在本研究中，我们将利用该方法合成多种环状有机化合物，这可能为合成许多复杂的有机结构提供一条简单的途径。

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.