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

有机和高分子化学项目的这个项目 是对设计和开发的研究的延续， 全新的反应、试剂和有机合成策略 综合，重点是战略层面的成环 方法论 新的和更有效的程序， 结构和生物学上重要化合物的合成 将提供扩展的基本理解 结构-反应性关系、反应理论和 机制等 本计划的第一部分是针对镍介导的 反应，包括立体和取代基的研究， 该反应的选择性，其在不对称合成中的用途， 全合成催化剂的变化和应用 紫杉烷类和蛇根烷类。 新反应 基于镍也提出了研究。 的第二部分 该计划旨在进一步调查照片- 诱导的双二烯环加成。 立体和取代基 选择性将结合上述进行评价 环加成重排反应合成及新方法 将被探索。 本计划的第三部分侧重于一个 芳烃烯烃环加成反应研究的继续 强大的战略级反应，提供了简化的 解决众多结构性问题。 这一努力将是 针对瑞替格尔烷酸的合成的完成， 月桂烯和灰蝶毒素II。

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.