Developing an Understanding of Asymmetric Induction

描述（由申请方提供）：本提案的广泛、长期目标是开发用于形成碳-碳键的新的高度对映选择性方法。机理研究，以简化这些方法的发展，并探讨催化剂的结构和反应性。本研究的一个中心主题是通过烷基、乙烯基、烯丙基、苯基和炔基基团对酮的不对称加成来对映选择性地生成手性季中心。虽然许多催化剂将促进这些基团以高对映选择性加成到醛上，但这些催化剂不促进类似的加成到酮上。我们已经开发了催化系统来解决这些重要的酮加成反应，允许容易地获得各种对映体富集的叔醇。 本建议的具体目标是：一。手性叔醇的催化不对称合成研究进展及II。一种实用的高烯丙醇催化不对称合成方法的开发。 该项目提出了新的方法来合成重要的手性结构单元，这些结构单元以前无法获得，但在与健康相关的应用中发现了实用性，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.