Catalytic allylation and benzylation methods

催化烯丙基化和苄基化方法

• 批准号: 1058855
• 负责人: Jon Tunge
• 金额: $ 42万
• 依托单位: University of Kansas Center for Research Inc
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-02-01 至 2015-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1058855&HistoricalAwards=false
• 关键词: Catalytic; allylation; benzylation; methods

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Jon Tunge of the Department of Chemistry at The University of Kansas will develop new decarboxylative coupling reactions. The proposed decarboxylative allylation and benzylation methods utilize CO2 release as a driving force for the synthesis of chemotypes that are prevalent in materials and pharmacologically important small molecules. Compared to other coupling methods, decarboxylative coupling offers the following benefits: i) carboxylic acids are abundant, ii) loss of CO2 provides an inherent large energetic driving force for reactions, iii) it avoids expensive, toxic, and highly basic reagents commonly employed for transmetallation, and iv) the byproduct is gaseous and therefore easily removed. At the completion of this project, it is expected that new methods for the synthesis of benzyl ketones, phenethylamines, benzyl coumarins, diaryl ethanes and asymmetric syntheses of gamma, delta-unsaturated esters, benzyl ketones, and diaryl methanes will have been developed. Furthermore, the proposed research will provide the chemical community with fundamental insight into these unique processes which involve the oxidative addition of C-O bonds. The broader impacts include advancing the fundamental knowledge of chemical reactions and providing synthetic chemists with environmentally friendly methods for the synthesis of enantioenriched compounds that are important intermediates in the synthesis of medicinally relevant natural products and small molecules. In addition to providing chemists with the tools to construct molecules in a highly selective manner, the proposed research will also provide a cornerstone for the training of undergraduate and graduate students who are society's future research scientists. Outreach via partnering with a small Midwestern school (Hastings College) to provide undergraduates research opportunities and free dissemination of "notes" on catalytic chemistry via the Tunge group website are just two of the ways that funding of this proposal will impact the broader community of upcoming scientists.

在这个由化学系化学合成计划资助的项目中，堪萨斯大学化学系的Jon Tunge教授将开发新的脱羧偶联反应。 所提出的脱羧烯丙基化和苄基化方法利用CO2释放作为合成化学型的驱动力，所述化学型在材料和非常重要的小分子中普遍存在。 与其他偶联方法相比，脱羧偶联提供了以下益处：i）羧酸是丰富的，ii）CO2的损失为反应提供了固有的大能量驱动力，iii）它避免了通常用于金属离子交换的昂贵的、有毒的和高碱性的试剂，以及iv）副产物是气态的，因此容易去除。 在该项目完成后，预计将开发出合成苄基酮、苯乙胺、苄基香豆素、二芳基乙烷以及不对称合成γ、δ-不饱和酯、苄基酮和二芳基甲烷的新方法。 此外，拟议的研究将为化学界提供对这些涉及C-O键氧化加成的独特过程的基本见解。 更广泛的影响包括推进化学反应的基础知识，并为合成化学家提供环境友好的方法来合成对映体富集的化合物，这些化合物是合成与医学相关的天然产物和小分子的重要中间体。 除了为化学家提供以高度选择性的方式构建分子的工具外，拟议的研究还将为培养作为社会未来研究科学家的本科生和研究生提供基石。 通过与中西部一所小型学校（黑斯廷斯学院）合作进行外展，为本科生提供研究机会，并通过Tunge集团网站免费传播催化化学“笔记”，这只是该提案的资助将影响更广泛的方式中的两种方式即将到来的科学家社区。