Organoiron Complexes in Organic Synthesis

这项工作的目标是双重的。1)二烯-铁三羰基配合物与附加的烯烃将偶联成螺环化合物。这种偶联反应允许立体定向结构的密集功能化分子，包含近端四元中心。该方法将应用于天然产物的核心结构的合成，甾酮和阿飞霉素。2)具有近端羟基的二烯-铁三羰基配合物可用于分子内立体选择性环化反应。二烯-铁络合物稳定由酸促进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配合物会导致不对称级联反应。通过这个奖项，有机和大分子化学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。皮尔森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（具有两个不可重叠的镜像）中形成碳-碳键，并且只能形成两种可能形式中的一种（单一对映体）的能力是当今制药工业面临的最重要问题之一。一旦开发成功，皮尔逊博士的工作可以应用于天然产物的合成，如地黄酮和阿飞霉素。在这项工作过程中训练的学生将获得制药行业所需的技能，该行业现在生产许多单一对映体化合物。

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.