Ligand Scaffold Optimization for Catalytic Asymmetric Hydroboration

本项目将继续致力于开发用于烯烃催化不对称硼化反应的手性自组装配体和催化剂。手性定向自组装使数十种甚至数百种独特配体支架的原位快速制备成为可能，从而允许以经典配体设计无法实现的方式对催化剂形貌进行微妙的结构操纵。虽然化学计量不对称硼氢化反应被广泛应用，但相对于其在不对称合成中的潜在应用，催化反应还不发达。对手性自组装配体进行组合型筛选，以发现新的有用的超分子催化剂。研究将进一步阐明这些催化剂成功的原因，为不对称催化提供新的基本见解。有了这个奖项，有机和大分子化学项目支持了内布拉斯加大学林肯分校化学系Takacs教授的研究。塔卡克斯教授?研究工作围绕着超分子催化剂的发展，使用自组装来产生大分子支架，定义有效催化所需的形状和特征，这是一种模仿生物催化剂的方法。该应用侧重于通过金属催化的硼氢化反应形成合成有用的多功能C-B键，这一反应在不对称合成中具有重要的未开发潜力。这种化学有希望用催化反应取代化学计量反应，从而为环境友好的化学合成方法做出贡献。该方法的成功发展将对制药和农业工业的合成产生影响。

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.