The design, synthesis and use of chiral ligands in various organic reactions: applications toward the asymmetric synthesis of natural products

手性配体的设计、合成和在各种有机反应中的应用：天然产物不对称合成的应用

• 批准号: 45988-2010
• 负责人: Keay, Brian
• 金额: $ 3.64万
• 依托单位: University of Calgary
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2011
• 资助国家: 加拿大
• 起止时间: 2011-01-01 至 2012-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=475053
• 关键词: design; synthesis; use; chiral; ligands

The goal of this proposal is to design, prepare and use new chiral ligands and chiral Lewis acids within certain key steps towards the asymmetric synthesis of natural products exhibiting interesting biological activity (anticancer properties, etc.). These new chiral entities are used in conjunction with metals (Pd, Rh, Ru, etc.) and Lewis acids (Al) in reactions that preferentially form one enantiomer in excess over the other. Other asymmetric reactions being studied include intra- and inter-molecular Diels Alder reactions, metal-catalyzed anion capture reactions and rhodium-catalyzed hydrogenations. The mechanism(s) of these reactions are studied using isotopes, a variety of NMR techniques and/or theoretical calculations (semi-empirical and DFT). We also execute some of these asymmetric reactions under high pressures and/or using microwaves.

本提案的目标是在某些关键步骤中设计，制备和使用新的手性配体和手性路易斯酸，以实现具有有趣生物活性（抗癌特性等）的天然产物的不对称合成。这些新的手性实体与金属（Pd, Rh， Ru等）和路易斯酸（Al）结合使用，在反应中优先形成过量的一种对映体。其他正在研究的不对称反应包括分子内和分子间的Diels Alder反应、金属催化的阴离子捕获反应和铑催化的氢化反应。使用同位素、各种核磁共振技术和/或理论计算（半经验和DFT）来研究这些反应的机理。我们也在高压和/或微波下进行一些不对称反应。