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

这项研究的重点是实施新的和未开发的反应，重点是有机金属化学、光化学和活性中间体，它们为合成中的一般问题提供了显著简化和有效的解决方案，允许促进对这些过程的理论、机理、结构-反应关系和选择性的基本理解，并提供了获得具有结构和/或生物重要性的新材料的途径。这项研究涉及三个主要领域。首先是芳烃-烯烃间环加成反应的发展，包括首次对不对称环加成反应的研究，并将其应用于已知的最复杂的四喹烷类化合物crinipellin的合成，以及合成新材料的新途径。第二个领域是开发新的过渡金属介导的反应，包括对特定天然产物的系统研究。第三个领域是对激进的促进重排的研究，以及尚未开发的、可能具有综合和机械意义的一般概念。这一计划的进一步意义来自于光化学和有机金属化学在开发更环保的工艺方面的巨大潜力，因为这些方法提供的试剂衍生废物很少或根本没有。有了这个续约奖，合成有机计划正在支持斯坦福大学化学系的保罗·A·温德博士的研究。温德教授将把工作重点放在有机合成的全新反应、试剂和策略的设计和开发上。研究的重点是实施新的或未开发的反应，这些反应提供了显着简化和结构和/或生物重要性。该项目的另一个重要意义来自于该项目的中心主题光化学和有机金属化学在开发更环保的工艺方面的巨大潜力，因为这些方法提供的试剂来源的废物很少或根本没有。

The focus of this research is the implementation of new and undeveloped reactions, with an emphasis on organometallic chemistry, photochemistry, and reactive intermediates, which provide significantly simplified and efficient solutions to general problems in synthesis, which allow for the advancement of the fundamental understanding of the theory, mechanism, structure-reactivity relationships, and selectivities of these processes, and which provide access to new materials of structural and/or biological importance. The research addresses three major areas. First is the development of arene-alkene meta-cycloadditions, including the first studies on asymmetric cycloaddition and the application to the synthesis of crinipellin, the most complex tetraquinane known, as well as a novel approach to new materials incorporating the fenestrane ring system. The second area is the development of new transition metal mediated reactions, including systematic studies of specific natural products. The third area is an investigation of radical facilitated rearrangements, and as yet undeveloped and potentially general concept of synthetic and mechanistic significance. Further significance of this program derives from the enormous potential of photochemistry and organometallic chemistry in development of more environmentally acceptable processes, as these methods provide little or no reagent derived waste. With this Renewal award, the Synthetic Organic Program is supporting the research of Dr. Paul A. Wender of the Department of Chemistry at Stanford University. Professor Wender will focus his work on the design and development of fundamentally new reactions, reagents, and strategies for organic synthesis. The emphasis of the research is on the implementation of new or undeveloped reactions which provide significantly simplified and structural and/or biological importance. Fu rther significance of this program derives from the enormous potential of photochemistry and organometallic chemistry, central themes of this project, in the development of more environmentally acceptable processes, as these methods provide little or no reagent derived waste.