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

本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，为合成中的一般问题提供了显着简化和有效的解决方案，从而提高了对这些过程的理论，机理，结构-反应性关系和选择性的基本理解，并且提供了获得具有结构和/或生物学重要性的新材料的途径。 研究涉及三个主要领域。 首先是芳烃-烯烃间位环加成的发展，包括对不对称环加成的首次研究和对crinipellin合成的应用，crinipellin是已知的最复杂的tetraquinane，以及引入fenestrane环系统的新材料的新方法。 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。 第三个领域是对自由基促进重排的研究，以及尚未开发的和潜在的具有合成和机械意义的一般概念。 该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，因为这些方法提供很少或没有试剂衍生的废物。 有了这个更新奖，合成有机计划是支持博士的研究。斯坦福大学化学系的温德说。 温德教授将专注于设计和开发全新的反应，试剂和有机合成策略。 研究的重点是实施新的或未开发的反应，这些反应具有显着简化的结构和/或生物学重要性。 该计划的进一步意义来自于光化学和有机金属化学的巨大潜力，该项目的中心主题，在开发更环保的过程中，因为这些方法提供很少或没有试剂衍生的废物。

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.