Formation of Organic Products by Oxidation of Metal Carbynes

金属卡宾氧化形成有机产物

• 批准号: 9421434
• 负责人: Lisa McElwee-White
• 金额: $ 22.8万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-02-01 至 1997-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9421434&HistoricalAwards=false
• 关键词: Formation; Organic; Products; Oxidation; Metal

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.

该奖项在佛罗里达大学化学系的Lisa McElwee-White博士的研究中，在无机，生物有机和有机金属化学计划中支持了有关有机合成中金属Carbynes的研究。 将开发前往七元和八元金属周，环丁酮，融合乙烯基环丙丙烷，呋喃，低聚物和其他产品的新途径。 激进阳离子和卡宾中间体是在钼和钨Carbynes光解过程中形成的。 重新排列和损失Carbyne配体后，可能会产生各种有机产品。 例如，带有束带烯烃和二enes的Carbyne取代基的复合物可以通过分子内ENE反应，环丙烷化，元理性或4+2 Cycloadition捕获中间体。 从激进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以产生环化产物。 金属通过三键与碳结合的有机金属化合物称为carbynes。 尽管对这些化合物的反应知之甚少，但它们尚未用于有机合成。 在这项研究中，将使用这种方法制备各种循环有机化合物，这可能为许多复杂的有机结构提供了简单的途径。