Ligand Scaffold Optimization for Catalytic Asymmetric Hydroboration

催化不对称硼氢化反应的配体支架优化

• 批准号: 0809637
• 负责人: James Takacs
• 金额: $ 42万
• 依托单位: University of Nebraska-Lincoln
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-07-01 至 2012-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0809637&HistoricalAwards=false
• 关键词: Ligand; Scaffold; Optimization; Catalytic; Asymmetric

This project will continue work on the development of chiral self-assembled ligands and catalysts for the catalytic asymmetric hydroboration of alkenes. Chirality-directed self-assembly enables the rapid in situ preparation of dozens, even hundreds, of unique ligand scaffolds and thus permits the subtle structural manipulation of catalyst topography in ways not available with classical ligand designs. While stoichiometric asymmetric hydroboration is widely used, the catalyzed reaction is underdeveloped relative to its potential utility in asymmetric synthesis. Combinatorial type screening of chiral self-assembled ligands will be carried out to identify new useful supramolecular catalysts. Studies to further elucidate the reasons for the success of these catalysts will be undertaken to provide new fundamental insight into asymmetric catalysis.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Takacs of the Department of Chemistry at the University of Nebraska-Lincoln. Professor Takacs? research efforts revolve around the development of supramolecular catalysts using self-assembly to generate macromolecular scaffolds that define the shape and characteristics required for efficient catalysis, an approach that mimics biological catalysts. This application focuses on the formation of synthetically useful and versatile C-B bonds via metal-catalyzed hydroboration, a reaction that holds significant untapped potential for asymmetric synthesis. Such chemistry holds the promise to replace a stoichiometric reaction protocol with a catalytic one and thus contribute to environmentally benign methods for chemical synthesis. Successful development of the methodology will have an impact on synthesis in the pharmaceutical and agricultural industries.

该项目将继续开发用于烯烃催化不对称氢硼化反应的手性自组装配体和催化剂。手性定向自组装能够快速原位制备数十种、甚至数百种独特的配体支架，从而允许以经典配体设计所不具备的方式对催化剂形貌进行微妙的结构操纵。尽管化学计量不对称氢化反应得到了广泛的应用，但相对于其在不对称合成中的潜在用途，催化反应还不够发达。将开展手性自组装配体的组合类型筛选，以寻找新的有用的超分子催化剂。为了进一步阐明这些催化剂成功的原因，将进行研究，以提供对不对称催化的新的基本见解。有了这个奖项，有机和高分子化学计划将支持内布拉斯加-林肯大学化学系的Takacs教授的研究。塔卡奇教授？研究工作围绕着开发超分子催化剂，使用自组装生成定义有效催化所需的形状和特征的大分子支架，这是一种模仿生物催化剂的方法。这一应用的重点是通过金属催化的氢硼化反应形成合成上有用且用途广泛的C-B键，该反应在不对称合成方面具有巨大的未开发潜力。这种化学有希望用催化反应协议取代化学计量反应协议，从而为环境友好的化学合成方法做出贡献。该方法的成功开发将对制药和农业中的合成产生影响。