Developing an Understanding of Asymmetric Induction

描述(由申请人提供)：这项建议的广泛、长期目标是开发形成碳-碳键的新的高度对映选择性的方法。通过机理研究简化了这些方法的发展，并探索了催化剂的结构和反应活性。这项研究的一个中心主题是通过烷基、乙烯基、烯丙基、苯基和炔基与酮的不对称加成反应生成手性四元中心。尽管许多催化剂能促进这些基团与醛的加成反应，但这些催化剂并不能促进酮的类似加成反应。我们已经开发了催化系统来处理这些重要的酮加成反应，允许容易地获得各种富含对映体的叔醇。 本建议的具体目的是：一、开发手性叔醇的催化不对称合成方法；二、开发实用的高烯丙醇催化不对称合成方法。 该项目介绍了合成重要的手性构建块的新方法，这些构建块以前无法获得，但在与健康相关的应用中有实用价值，特别是在手性药物的合成中。

DESCRIPTION (provided by applicant): The broad, long-term objectives of this proposal are to develop new highly enantioselective methods for the formation of carbon-carbon bonds. Mechanistic studies are employed to streamline the development of these methods and to probe the catalyst structure and reactivity. A central theme of this research is the enantioselective generation of chiral quaternary centers through asymmetric addition of alkyl, vinyl, allyl, phenyl, and alkynyl groups to ketones. Although many catalysts will promote the addition of such groups to aldehydes with high enantioselectivity, these catalysts do not promote the analogous additions to ketones. We have developed catalytic systems to address these important ketone addition reactions, allowing easy access to a variety of enantioenriched tertiary alcohols. The Specific Aims of this proposal are: I. Development of a Catalytic Asymmetric Synthesis of Chiral Tertiary Alcohols and II. Development of a Practical Catalytic Asymmetric Synthesis of Homoallylic Alcohols. This project presents new methods to synthesize important chiral building blocks that were not previously accessible, but find utility in health-related applications, particularly in the synthesis of chiral pharmaceutical agents.