Developing an Understanding of Asymmetric Induction

加深对不对称感应的理解

• 批准号: 6758606
• 负责人: PATRICK J WALSH
• 金额: $ 38.85万
• 依托单位: UNIVERSITY OF PENNSYLVANIA
• 依托单位国家: 美国
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-09-01 至 2007-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6758606
• 关键词: aldehydes; alkylation; allyl compound; catalyst; chemical addition; chemical structure; chemical synthesis; cyclic ketone; ligands; method development; molecular asymmetry; nuclear magnetic resonance spectroscopy; stereochemistry

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.

描述（由申请人提供）：本提案的广泛，长期目标是开发新的高度对映选择性的碳-碳键形成方法。利用机理研究来简化这些方法的发展，并探索催化剂的结构和反应性。本研究的一个中心主题是通过不对称加成烷基、乙烯基、烯丙基、苯基和炔基到酮的手性季中心的对映选择性生成。虽然许多催化剂会促进这些基团加成到具有高对映选择性的醛上，但这些催化剂不会促进类似的加成到酮上。我们已经开发了催化系统，以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叔醇。