STEROSELECTIVE SYNTHESIS OF EXOCYCLIC OLEFINS

外环烯烃的立体选择性合成

• 批准号: 3291238
• 负责人: EI-ICHI NEGISHI
• 金额: $ 14.3万
• 依托单位: PURDUE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1986
• 资助国家: 美国
• 起止时间: 1986-07-01 至 1989-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3291238
• 关键词: alkenes; drug design /synthesis /production; isomer; prostacyclins; stereochemistry

It is proposed to systematically develop stereospecific and general methods for the synthesis of exocyclic alkenes, that are applicable to the preparation of both E and Z isomers, based on stereo- and regioselective carbometallation reactions of alkynes. Four conceptually different approaches that are complementary to each other will be investigated. Despite the growing significance of various stereodefined exocyclic alkenes of medicinal interest, such as prostacyclin, carbacyclin, zoapatanol, pumiliotoxin B, and fusidic acid, synthetic chemists are still without general and selective methodologies that can readily provide satisfactory procedures for efficient and selective syntheses of various types of exocyclic alkenes without requiring separate developments of specific procedures for individual cases. The proposed investigation is expected to provide, for the first time, such a general and selective methodology. In part to provide novel, efficient, and stereoselective procedures and in part to demonstrate the practical usefulness of the above-mentioned methodology, carbacyclin and pumiliotoxin B will be synthesized using the above-mentioned methodology.

建议系统地开发立体特异性和通用方法 用于合成环外烯烃，适用于 基于立体选择性和区域选择性制备 E 和 Z 异构体 炔烃的碳金属化反应。 四个概念不同 将研究相互补充的方法。 尽管各种立体定义的环外烯烃的重要性越来越大 具有药用价值，例如前列环素、碳环素、佐阿帕醇、 普米利奥毒素B和夫西地酸，合成化学家目前还没有 可以轻松提供令人满意的通用和选择性方法 高效和选择性合成各种类型的程序 环外烯烃无需单独开发特定的 个别案件的程序。 拟议的调查预计将 首次提供这样一种通用且有选择性的方法。 部分是为了提供新颖、高效和立体选择性的程序，并在 部分展示上述内容的实际用途 方法，将使用以下方法合成碳环素和普米利奥毒素 B 上述方法论。