Bronsted Acid Catalysis in Enantioselective Acyl Substitution

对映选择性酰基取代中的布朗斯台德酸催化

• 批准号: 1012979
• 负责人: Vladimir Birman
• 金额: $ 32.48万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-09-15 至 2015-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1012979&HistoricalAwards=false
• 关键词: Bronsted; Acid; Catalysis; Enantioselective; Acyl

The Chemical Catalysis Program supports Professor Vladimir B. Birman of Washington University for a project that will explore the application of Brønsted acids to catalytic, asymmetric acyl substitution reactions, such as enantioselective O- and S-acylation and enantioselective alcoholysis of chiral acyl donors. The two basic modes of activation that will be applied to several classes of acyl donors are acid-assisted acyl transfer catalysis and direct Brønsted acid catalysis using axially chiral phosphoric acids.The acyl transfer catalysis will utilize primarily achiral carboxylic acids in combination with amidine-based enantioselective acylation catalysts previously developed in the Birman laboratory. These studies will lead to the development of new methods for the nonenzymatic kinetic resolution (KR), dynamic kinetic resolution (DKR), desymmetrization and deracemization of several classes of substrates. The availability of a simple transition state model will be helpful for introducing students to the basics of asymmetric catalysis. Professor Vladimir B. Birman will work in a topical area called asymmetric organocatalysis that is having considerable potential impact in both industry and academia. The research will lead to a better understanding of non-covalent interactions in the chemical community. The broader scientific impact, for process development outside of academia, could be quite significant. Graduate and undergraduate students will be provided more diverse training in synthetic organic chemistry. The recently developed protocol for the DKR of 4-aryl-azlactones is operationally simple, utilizes easily obtainable starting materials and catalysts, and presents an opportunity to discuss many fundamental concepts of organic chemistry. This makes it an ideal candidate for incorporation into the undergraduate laboratory curriculum at Washington University. These steps will further improve the quality of the graduate and undergraduate programs in chemistry at Washington University and help build its strength as one of the leading research institutions in the Midwest.

化学催化计划支持华盛顿大学的弗拉基米尔·B·比尔曼教授的一个项目，该项目将探索溴酸在催化的不对称酰基取代反应中的应用，例如手性酰基供体的不对称O-和S-酰化以及不对称醇解。应用于几类酰基给体的两种基本活化模式是酸辅助的酰基转移催化和使用轴向手性磷酸的直接布朗斯特酸催化。酰基转移催化将主要利用无手性羧酸和先前在比尔曼实验室开发的基于酰胺的对映选择性酰化催化剂。这些研究将为几类底物的非酶动力学拆分(KR)、动态动力学拆分(DKR)、去对称化和去对映体拆分提供新的方法。一个简单的过渡态模型的可用性将有助于向学生介绍不对称催化的基础知识。弗拉基米尔·B·比尔曼教授将在一个名为不对称有机催化的热门领域工作，该领域在工业界和学术界都有相当大的潜在影响。这项研究将有助于更好地理解化学界中的非共价相互作用。对于学术界以外的过程开发来说，更广泛的科学影响可能是相当重大的。将为研究生和本科生提供更多样化的合成有机化学培训。最近开发的4-芳基氮内酯的DKR方案操作简单，使用了容易获得的起始材料和催化剂，并提供了一个讨论许多基本有机化学概念的机会。这使得它成为纳入华盛顿大学本科实验室课程的理想人选。这些措施将进一步提高华盛顿大学化学研究生和本科生课程的质量，并有助于增强其作为中西部领先研究机构之一的实力。