Synthetic and Mechanistic Studies of Organometalloids

有机类金属的合成与机理研究

• 批准号: 8814876
• 负责人: Hans Reich
• 金额: $ 48.9万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-12-01 至 1993-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8814876&HistoricalAwards=false
• 关键词: Synthetic; Mechanistic; Studies; Organometalloids

The Organic Synthesis Program will provide support to Dr. Hans J. Reich in the Department of Chemistry at the University of Wisconsin in Madison. The work will develop the synthetic potential of the main group by unraveling the nature of some of the intermediates and applying this knowledge to develop greater synthetic control. The synthesis of the complex molecules utilized by modern agriculture and medicine requires highly sophisticated synthetic methodology. This research is in several areas of main group organometalloid and organometallic chemistry. Specifically, experiments aimed at elucidating the mechanism of some important metathesis reactions of organolithium reagents, the metal-halogen exchange and the transmetallation reaction of organotin compounds, are described. Since these reactions are widely used in preparative organic chemistry it is important to understand them mechanistically. The experiments described will clarify the role that ate complexes play in the chemistry of organolithium reagents, and will establish whether the complexes themselves are useful carbanion donors. A new technique for determining geometry of nucleophilic attack at non-stereogenic centers (divalent tellurium) will be examined. An exploratory study will establish whether a dynamic NMR technique which has provided detailed information concerning the mechanism of the degenerate Li/I exchange between phenyllithium and iodobenzene, can also be used to study enolate reactions. The second part concerns the design of a chiral electrophilic selenenylation agent. The reagent is designed to utilize the geometry of hypervalent organoselenium species thought to be intermediates in the electrophilic addition of R-Se+ species to olefins. The process, if successful, would provide a method for asymmetric oxidation of olefins to nonracemic allyl alcohols or lactones. A third part involves the continuation of ongoing research to investigate the potential of using silyl ketones as precursors to carbonyl ylides.

有机合成计划将为汉斯博士提供支持。 华盛顿大学化学系的J.赖希说， 麦迪逊的威斯康星州。 这项工作将开发合成 通过揭示一些主要群体的性质， 中间体和应用这些知识来开发 更大的综合控制。 配合物的合成 现代农业和医学所利用的分子需要 高度复杂的合成方法 本研究是在几个领域的主要群体有机类 和有机金属化学 具体而言，实验旨在 在阐明一些重要的复分解机制方面 有机锂试剂的反应，金属-卤素交换 以及有机锡化合物的金属转移反应， 介绍了 由于这些反应被广泛应用于 制备有机化学重要的是要了解 他们机械地。 所描述的实验将阐明 ATE复合物在化学中的作用 有机锂试剂，并将确定是否 络合物本身是有用的碳负离子供体。 一个新 测定亲核进攻几何构型技术. 将检查非立体中心（二价碲）。 一项探索性研究将确定动态核磁共振是否 该技术提供了有关 简并Li/I交换机制 苯基锂和碘苯，也可用于研究 烯醇化反应 第二部分涉及手性亲电分子的设计 硒化剂。 该试剂旨在利用 超价有机硒物种的几何形状被认为是 R-Se+物种亲电加成中间体， 烯烃。 这个过程如果成功的话， 用于烯烃不对称氧化成非外消旋烯丙基 醇或内酯。 第三部分涉及继续进行研究， 研究使用甲硅烷基酮作为前体的潜力 羰基叶立德。