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

这项研究的重点是促进对最近引入的反应的机理和选择性的了解，新发现的反应的研究，以及新反应的鉴定，包括分子间的烯基和烯基-乙烯基环丙烷(VCP)[5+2]环加成；烯丙基-VCP-CO[5+2+1]环加成；不对称[5+2]环加成；不对称[5+2]环加成；生成VCP和VCB(乙烯基环丁烷)的变式反应；二烯、烯烃和CO的[4+2+1]环加成；二烯-二烯-CO[2+2+1]环加成；基于二烯和烯的3-组分反应；烯丙基环丁烷的[6+1]反应；羰基转位；[5+1+2+1]环加成；[5+1+2+1]环加成；基于二烯和烯的3-组分反应；烯丙基环丁烷的[6+1]反应；羰基烯丙基转位；[5+1+2+1]环加成；[5+1+2+1]环加成；[5+2+1]环加成[3+2]/[5+1]反应；以及使用四组分的环加成物作为催化和分子识别的配体。有了这个续期奖，有机和高分子化学计划将支持斯坦福大学化学系的Paul A.Wender博士的研究和教育活动。温德教授将专注于有机合成的全新反应、试剂和策略的设计或发现和开发。该项目的继续重点是确定新的反应，因为新的反应使新的合成策略成为可能，即使不是理想的合成(高产率、步骤经济、资源有效、操作简单和环境可接受)，也可以更好地合成具有理论、材料或医药价值的靶标。特别强调催化反应，特别是那些在没有催化剂的情况下被禁止或难以实现的过程。新反应的引入提供了思考合成问题的新方法，新的工艺选择可以最大限度地减少或避免环境问题步骤和工艺效率低下，而且通常还提供了新的机制和见解，增加了我们对成键、结构和反应性的基本知识。该项目具有更广泛的影响，通过对博士后参与者的培训，开展从面向高中生的教育。对化学、制药和农业的科学影响也将增加。

The focus of this research is to advance understanding of the mechanisms and selectivities of recently introduced reactions, on the investigation of newly identified reactions, and on the identification of new reactions including intermolecular allenyl- and alkenyl-vinylcyclopropane (VCP) [5+2] cycloadditions; allenyl-VCP-CO [5+2+1] cycloadditions; asymmetric [5+2] cycloadditions; metathetical processes for the generation of VCPs and VCBs (vinylcyclobutanes); [4+2+1] cycloadditions of dienes, alkenes, and CO; allene-diene-CO [2+2+1] cycloadditions; 3-component reactions based on dienes and allenes; [6+1] reactions of allenylcyclobutanes; carbonylative allenyl ether transpositions; [5+1+2+1] cycloadditions; [3+2]/[5+1] reactions; and the use of 4-component cycloadducts as ligands for catalysis and molecular recognition.With this renewal award, the Organic and Macromolecular Chemistry Program is supporting the research and educational activities of Dr. Paul A. Wender in the Department of Chemistry at Stanford University. Professor Wender will focus his work on the design or discovery and development of fundamentally new reactions, reagents, and strategies for organic synthesis. The continuing emphasis of the project is on the identification of new reactions as new reactions enable new synthetic strategies and better if not ideal syntheses (high yielding, step economical, resource effective, operationally simple and environmentally acceptable) of targets of theoretical, materials, or medicinal value. A special emphasis is placed on catalyzed reactions, especially processes that in the absence of catalyst are forbidden or difficult to achieve. The introduction of new reactions offers new ways to think about synthetic problems, new process options that could minimize or avoid environmentally problematic steps and process inefficiencies, and often new mechanisms and insights that add to our basic knowledge of bonding, structure, and reactivity. The project has broader impact by engaging in education from outreach to high school students through the training of postdoctoral participants. Scientific impact on the chemical, pharmaceutical and agricultural industries will also accrue