ALKYNYLIODONIUM SALTS IN ORGANIC SYNTHESIS

描述：（逐字摘自申请人摘要）持续的 炔基碘鎓盐介导的碳环化的发展和 杂环化反应，以及该化学在总反应中的应用 计划合成具有治疗前景的天然产物。一个简洁的 从防己科植物中合成有效的抗白血病原理， 帕瑞托酮，将被启动。此外，合成程序指导 结构新颖的 VCAM-1 诱导抑制剂 halichlorine 将 开始。亲核引发的新级联环化的发现 除了具有适当位置的不饱和的炔基碘盐之外 功能将构成拟议研究的中心主旨。这些 多步转换将导致各种高效组装 常见的多环系统，包括二奎烷， 前卡内烷、α-亚甲基环戊酮、环戊烷苯并呋喃、 和环戊烷吲哚。在一个单独的脉络中，一代和 甲硅烷氧基亚烷基卡宾的高效碳环化反应将是 调查了。这些发展研究将取得有希望的进展 然后将该方法应用于同源化合物的合成 目标。总而言之，这些研究将引入新的、简洁的 多环有机小分子的制备技术 通常寻求作为药物先导化合物的类型。

Description: (Verbatim from the Applicant's Abstract) The continuing development of alkynyliodonium salt-mediated carbocyclization and heterocyclization reactions, and application of this chemistry to the total synthesis of therapeutically promising natural products, is planned. A concise synthesis of the potent antileukemic principle from Menispermaceae, pareitropone, will be initiated. In addition, a synthesis program directed toward the structurally novel VCAM-1 induction inhibitor halichlorine will commence. The discovery of new cascade cyclizations triggered by nucleophilic addition to alkynyliodonium salts bearing appropriately positioned unsaturated functionality will constitute a central thrust of the proposed research. These multi-step transformations will lead to efficient assembly of a variety of commonly encountered polycyclic ring systems, including diquinanes, precapnellanes, alpha-methylenecyclopentanones, cyclopentannelated benzofurans, and cyclopentannelated indoles. In a separate vein, the generation and productive carbocyclization of silyloxyalkylidene carbenes will be investigated. Promising advances in these developmental studies will be followed by application of the methodology toward the synthesis of cognate targets. Taken together, these studies will introduce new and concise techniques for preparing small polycyclic organic molecules of the type typically sought as pharmaceutical leads.