Approaches to Improved Synthesis Design: Mechanistic and Synthetic Studies on New Annelation Methods (Chemistry)

改进合成设计的方法：新退火方法的机理和合成研究（化学）

• 批准号: 8706051
• 负责人: Paul Wender
• 金额: $ 64.23万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-06-01 至 1992-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8706051&HistoricalAwards=false
• 关键词: Approaches; Improved; Synthesis; Design; Mechanistic

This project in the Organic and Macromolecular Chemistry Program is a continuation of studies on the design and development of fundamentally new reactions, reagents, and strategies for organic synthesis, with an emphasis on strategy level ring-forming methodology. New and more efficient procedures for the total synthesis of structurally and biologically important compounds will be provided extending understanding of fundamental structure-reactivity relationships, reaction theory and mechanisms. The first part of this program is directed at nickel-mediated reactions and includes studies on the stereo- and substituent- selectivity of this reaction, its use in asymmetric synthesis, catalyst variations and applications toward the total synthesis of asteriscanolide, taxanes, and ophiobolanes. New reactions based on nickel are also proposed for study. The second part of this program is directed at the further investigation of photo- induced bis-diene cycloadditions. Stereo- and substituent selectivities will be evaluated in connection with the above synthetic work and a new method for cycloadduct rearrangement will be explored. The third section of this program focuses on a continuation of studies on the arene olefin cycloaddition, a powerful strategy level reaction which has provided simplified solutions to numerous structural objectives. This effort will be directed at the completion of synthesis of retigeranic acid, laurenene, and grayanotoxin II.

有机和高分子化学计划中的这个项目是关于有机合成的全新反应、试剂和策略的设计和开发的继续研究，重点是策略级成环方法。将提供新的和更有效的全合成方法，以扩大对基本结构-反应关系、反应理论和机理的理解。该计划的第一部分针对镍介导的反应，包括对该反应的立体选择性和取代基选择性的研究，它在不对称合成中的应用，催化剂的变化以及在总合成海星内酯、紫杉烷和蛇床子烷方面的应用。还提出了基于镍的新反应以供研究。本程序的第二部分旨在进一步研究光诱导的双二烯环加成反应。将结合上述合成工作对立体选择性和取代基选择性进行评价，并将探索一种新的环加成重排方法。本计划的第三部分侧重于芳烃环加成反应的继续研究，这是一种强大的策略级反应，为许多结构目标提供了简化的解决方案。这项工作的目标是完成雷公藤酸、月桂烯和灰霉毒素II的合成。