Organoiron Complexes in Organic Synthesis

这项工作有两个目标。 1)具有附加烯烃的二烯-三羰基铁络合物将偶联以制备螺环化合物。 该偶联反应允许立体特异性构建含有近端季中心的密集官能化分子。 该方法将应用于天然产物stemodinone和aphidicolin的核心结构的合成。 2)具有近端羟基的二烯-三羰基铁络合物将用于立体选择性分子内环化反应。 二烯-铁络合物稳定由酸促进的羟基离子化形成的阳离子，从而实现立体控制的分子内环化。 在这些环化反应中使用光学纯的复合物应该会导致不对称级联反应。有了这个奖项，有机和大分子化学计划正在支持凯斯西储大学化学系的Anthony J. Pearson博士的研究。 Pearson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（具有两个不可重叠的镜像），并且仅产生两种可能形式中的一种（单一对映异构体）是当今制药工业面临的最重要的问题之一。 皮尔逊博士的工作可以应用于合成天然产物，如stemodinone和aphidicolin。 在这项工作的过程中培训的学生将获得制药行业所需的技能，现在生产一些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.