METAL CATALYZED CARBON--CARBON BOND FORMING REACTIONS

合成有机化学继续发挥主导作用， 优化生物活性结构的治疗活性。 我们组的研究方向是小说的发展 过渡金属催化的碳-碳键形成反应 涉及无环底物的碳环化。 我们的目标是提供 用于有机合成的新型环化方法， 常见的有机官能团，并在金属中进行催化。 我们 方法是解决两个机械方面的问题， 环化以及新的简单的合成应用 方法. 在此期间，我们将继续我们的 催化金属介导的碳环化反应的研究 三烯和四烯。 这些研究旨在利用 结构和反应性的有机金属中间体，以控制 碳-碳键立体化学和区域化学过程 两个配位双键之间的结构， 环化反应 这种竞争性的更新描述了小说的持续发展 基于催化过渡金属介导的合成方法 碳环化 拟议的研究是基础研究的混合 (e.g.,底物，捕获试剂，简单非对映选择性，1，2- 和1，3-立体诱导，对映选择性环化，新金属 催化剂等）催化金属介导的碳环化 三烯和四烯，和简单的应用程序的方法， 生物活性和/或医学相关环的合成 系统. 未来四年的拟议研究已细分 分为四个部分。 第一部分是集中在合成应用的 铁催化的三烯碳环化反应及其进展 互补的钴催化环化反应 第2部分描述了 钯催化的四烯碳环化的持续发展。 本节中提出的研究重点是应用于 前列腺素类化合物的合成以及与结构相关的模型研究 氢化奥林和离子载体中心环的问题 抗生素Tetronasin（ICI 139603）。 以发展为导向的研究 还描述了铑催化的四烯碳环化反应。 部分 3描述了制备对映体纯的碳环和杂环化合物的努力， 环系统在立体控制的方式，通过使用 可回收的手性助剂。 第4部分描述了对 定义其他新的，但机械相关的，碳环化 反应.

Synthetic organic chemistry continues to play a dominant role in optimizing the therapeutic-activity of biologically active structures. Research in my group is directed toward the development of novel transition-metal-catalyzed carbon-carbon bond forming reactions applied to the carbocyclization of acyclic substrates. Our goal is to provide novel cyclization methodologies for organic synthesis that utilize common organic functional groups and proceed catalytic in metal. Our approach has been to address both mechanistic aspects of the cyclizations as well as simple synthetic applications of the new methods. During the tenure of this grant we will continue our investigations into catalytic metal-mediated carbocyclizations of trienes and tetraenes. The studies are designed to exploit the unique structure and reactivity of organometal intermediates to control the stereochemical and regiochemical course of carbon-carbon bond construction between two coordinated double bonds in the context of cyclization reactions. This competing renewal describes the continuing development of novel synthetic methodologies based upon catalytic transition-metal-mediated carbocyclizations. The proposed research is a blend of basic studies (e.g., substrates, trapping reagents, simple diastereoselectivity, 1,2- and 1,3- stereoinduction, enantioselective cyclization, new metal catalysts, etc.) on the catalytic metal-mediated carbocyclizations of trienes and tetraenes, and simple applications of the methodologies to the synthesis of biologically-active and/or medicinally-relevant ring systems. The proposed studies for the next four years are broken down into four parts. Part I is focussed on synthetic applications of the iron-catalyzed ene carbocyclizations of trienes and on the development of a complementary cobalt-catalyzed cyclization. Part 2 describes the continued development of palladium-catalyzed tetraene carbocyclizations. The proposed research in this section focuses on an application to the synthesis of prostanoids and on model studies relevant to the structural problems in the hydroazulenes and the central ring in the ionophore antibiotic Tetronasin (ICI 139603). Studies directed toward development of rhodium-catalyzed tetraene carbocyclizations is also described. Part 3 describes efforts to prepare enantiopure carbocyclic and heterocyclic ring systems in a stereocontrolled fashion through the use of recoverable chiral auxiliaries. Part 4 describes investigations into defining other new, but mechanistically related, carbocyclization reactions.