Transition Metal Metallacycles: Synthesis via Remote Intramolecular C-H Bond Activation and Utility in Main-GroupHeterocyclic Synthesis

大卫博士R.俄勒冈州大学化学系的泰勒是 由化学合成有机化学计划支持 合成用金属杂环化合物发展司 基团杂环通过远程分子内C-H键活化。一系列 存在一个或多个位点的前过渡金属乙烯基络合物 对于分子内C-H活化，并且总是包括至少一个 将准备可用于伽马激活的位点。化疗- 和区域选择性的C-H活化反应，通过这些 复合体将被确定。通过系统的变化， 乙烯基上取代基的位置和性质以及 过渡金属的性质，理解空间位阻和 将开发有利于远程激活的电子因素。的 由此产生的信息将用于协助合理准备 金属环配合物，特别是带有金属环丁烯的 通过使用现有的合成方法无法获得的取代基模式 程序.这些金属环配合物将被利用， 重点是开发络合物在催化剂中的应用， 杂环化合物的形成。 过渡金属通常用于制备重要的 有机化学品该项目旨在开发新的方法， 一系列迄今难以获得的物种。这些“杂环” 化合物具有重要的实验室、工业和生物学意义。 此外，该项目还将探索碳氢化合物的活化 远离过渡金属的键。这一阶段的 调查将提供关于有机 化合物可被过渡金属活化。

Dr. David R. Tyler, Department of Chemistry, University of Oregon is supported by the Synthetic Organic Chemistry Program of the Chemistry Division for the development of metallacycles for the synthesis main group heterocycles by remote intramolecular C-H bond activation. A series of early transition metal vinyl complexes that present one or more sites for intramolecular C-H activation and that always include at least one site that is accessible for gamma-activation will be prepared. The chemo- and regio- selectivity of the C-H activation reactions by these complexes will be determined. Through systematic variation in the placement and nature of the substituents on the vinyl group and the nature of the transition metal, an understanding of the steric and electronic factors favoring remote activation will be developed. The resulting information will be used to assist in the rational preparation of metallacyclic complexes, particularly metallacyclobutenes bearing substituent patterns unavailable through the use of existing synthetic procedures. There metallacyclic complexes will be exploited, with primary focus on the development of catalytic uses of the complexes in the formation of heterocyclic compounds. Transition metals are often used to effect the preparation of important organic chemicals. This project aims at developing new methods to prepare a variety of heretofore difficult to obtain species. These `heterocyclic` compounds have great laboratory, industrial, and biological significance. In addition, this project will explore the activation of carbon-hydrogen bonds that are remote from a transition metal. This phase of the investigation will provide fundamental information on how organic compounds can be activated by transition metals.