Organoiron Complexes in Organic Synthesis

这项工作的目标有两个。1)将二烯铁三羰基络合物与附加的烯烃偶联，得到螺环化合物。这种偶联反应允许立体特异地构建含有近端四元中心的稠密官能化分子。这一方法将被应用于天然产物的核心结构的合成，如菊花酮和除草剂。2)具有近端羟基的二烯-铁三羰基络合物将用于立体选择性的分子内环化反应。二烯-铁络合物稳定由酸促进的羟基电离形成的阳离子，从而实现立体控制的分子内环化反应。在这些环化反应中使用光学纯的络合物应该会导致不对称的级联反应。凭借这一奖项，有机化学和高分子化学计划支持凯斯西储大学化学系的Anthony J.Pearson博士的研究。皮尔逊博士将探索有机铁试剂的立体选择性环化反应。在手性分子中形成碳-碳键的能力(有两个不可重叠的镜像)并且只形成两种可能形式中的一种(单一对映体)是当今制药业面临的最重要的问题之一。开发出来后，皮尔逊博士的工作可以应用于天然产物的合成，如金龟子酮和除草剂。在这项工作过程中接受培训的学生将获得制药业所需的技能，制药业现在生产许多单一的对映体化合物。

The objectives of this work are two fold. 1) Diene-iron tricarbonyl complexes with appended olefins will be coupled to make spirocyclic compounds. This coupling reaction allows stereospecific construction of densely functionalized molecules that contain proximal quaternary centers. This methodology will be applied to the synthesis of the core structures of the natural products, stemodinone and aphidicolin. 2) Diene-iron tricarbonyl complexes with proximal hydroxyl groups will be used in stereoselective intramolecular cyclization reactions. The diene-iron complex stabilizes cations formed by acid promoted ionization of the hydroxyl group allowing stereocontrolled intramolecular cyclizations to be effected. Use of optically pure complexes in these cyclizations should lead to asymmetric cascade reactions.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Anthony J. Pearson of the Department of Chemistry at Case Western Reserve University. Dr. Pearson will explore stereoselective cyclization reactions of organoiron reagents. The ability to form carbon-carbon bonds in molecules which are chiral (have two nonsuperimposable mirror images) and make only one of the two possible forms (a single enantiomer) is one of the most important problems facing the pharmaceutical industry today. When developed, Dr. Pearson's work could be applied to the synthesis of natural products such as stemodinone and aphidicolin. Students trained during the course of this work will gain skills needed by the pharmaceutical industry which now produces a number of single enantiomer compounds.