Catalytic Enantioselective Olefin Metathesis Reactions

催化对映选择性烯烃复分解反应

• 批准号: 7028355
• 负责人: RICHARD R SCHROCK
• 金额: $ 40.04万
• 依托单位: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-03-01 至 2008-02-29
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7028355
• 关键词: alkenes; catalyst; chemical synthesis; cyclization; molecular rearrangement; molybdenum; stereochemistry; tungsten

DESCRIPTION (provided by applicant): Olefin metathesis converts relatively simple olefinic substrates to complex asymmetric compounds in a clean and efficient manner, and has been shown to eliminate many steps in a synthesis of a target organic molecule. Olefin metathesis is thus of considerable interest in the synthesis of medicinally and biologically significant molecules. With more efficient and selective reactions and catalysts available, therapeutic candidates can be made available to the public more readily and in a more cost effective manner. The main objectives of this program involve the design, synthesis, characterization, and mechanistic exploration of a wide variety of new asymmetric molybdenum- and tungsten-based olefin metathesis catalysts. In addition, these novel chiral catalysts will be used to carry out unique enantioselective C-C bond forming reactions of significant interest to synthetic organic chemists. Particular emphasis will be placed on reactions that lead to the formation of products that cannot be prepared easily through any of the available catalytic or enzymatic routes. Among the reactions of interest will be asymmetric ring-closing, ring-opening, and cross metathesis reactions. In a number of cases the utility of the newly developed reactions will be demonstrated through application to the preparation of biologically significant molecules. The catalysts, methods and concepts that emerge from the proposed studies will allow chemists to access a wider range of molecules of biological interest more efficiently, reliably, and in a highly enantioselective fashion.

描述（由申请人提供）：烯烃复分解以清洁和有效的方式将相对简单的烯烃底物转化为复杂的不对称化合物，并且已经显示出消除了目标有机分子合成中的许多步骤。因此，烯烃复分解在合成具有医学和生物学意义的分子中具有相当大的兴趣。随着更有效和选择性的反应和催化剂的可用，治疗候选物可以更容易地和以更具成本效益的方式提供给公众。 该计划的主要目标涉及各种新型不对称钼和钨基烯烃复分解催化剂的设计，合成，表征和机理探索。此外，这些新的手性催化剂将用于进行独特的对映选择性的C-C键形成反应的显着兴趣的合成有机化学家。特别强调的是，将被放置在导致产品的形成，不能通过任何可用的催化或酶的途径容易地制备的反应。感兴趣的反应将是不对称的闭环、开环和交叉复分解反应。在许多情况下，新开发的反应的效用将通过应用于制备生物学上重要的分子来证明。 从拟议的研究中出现的催化剂，方法和概念将使化学家能够更有效，更可靠地以高度对映选择性的方式获得更广泛的生物分子。