Organoiron Complexes in Organic Synthesis

[308105]本研究的重点是开发利用各种有机铁配合物形成碳碳键的新方法。我们将研究有机铁化学的四个方面。第一个方面研究了二烷基配合物产生自由基的新方法，以及它们与垂坠的烯烃基团形成碳环体系的分子内偶联。这是有机金属自由基在合成过程中的首次应用。第二方面研究了铁促进二炔和炔羰基环化形成环戊二烯铁配合物和环戊烯酮的扩展和应用。第三个领域探索分子内碳亲核试剂在环己二烯离子上的添加，为构建密集功能化分子提供重要的新方法。最后一个方面是利用有机铁片段在八元环多功能化过程中控制立体化学的能力，这在传统上是难以处理的；有机金属化学的应用为构象和立体化学控制提供了解决方案。有了这个奖，合成有机项目支持了凯斯西储大学化学系安东尼·j·皮尔森博士的研究。皮尔逊教授将把他的工作重点放在合成方法学领域，开发利用各种有机铁配合物形成碳-碳键的新方法。＊＊＊

9308105 Pearson The focus of this research is the development of new methods for carbon-carbon bond formation using a variety of organoiron complexes. There are four specific aspects of organoiron chemistry that will be studied. The first aspect investigates new protocols for the generation of free radicals from dienyliron complexes and their intramolecular coupling with pendant olefinic groups to form carbocyclic ring systems. This represents the first application of organometallic free radicals in synthetically useful processes. The second aspect studies extensions and applications of iron-promoted carbonylative annulation of diynes and enynes for formation of cyclopentadienoneiron complexes and cyclopentenones. The third area explores intramolecular carbon nucleophile additions to cyclohexadienyliron cations to provide important new methods for the construction of densely functionalized molecules. The final aspect exploits the ability of an organoiron moiety to control stereochemistry during multiple functionalization of eight-membered rings, which are traditionally difficult to handle; the use of organometallic chemistry provides solutions to problems of conformational and stereochemical control. %%% With this award, the Synthetic Organic Program is supporting the research of Dr. Anthony J. Pearson of the Department of Chemistry at Case Western Reserve University. Professor Pearson will focus his work in the area of synthetic methodology developing new methods for carbon-carbon bond formation using a variety of organoiron complexes. ***