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

点击翻译按钮获取中文摘要

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.