Ruthenium Catalyzed Oxidation and Addition Reactions

钌催化的氧化和加成反应

• 批准号: 6504626
• 负责人: CHAE S YI
• 金额: $ 14.5万
• 依托单位: MARQUETTE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-08-01 至 2005-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6504626
• 关键词: alcohols; alkenes; alkynes; carbonyl compound; catalyst; chemical addition; chemical synthesis; cycloalkene; diene; oxidation reduction reaction; ruthenium

DESCRIPTION (provided by applicant): The transition metal-catalyzed selective oxidation of unreactive carbon-hydrogen bonds is a direct method or forming alcohols and carbonyl compounds from hydrocarbons under mild conditions. Inspired by remarkable catalytic activity of metalloenzymes in nature, extensive research has been focused on the development of practical catalytic methods for C-H bond oxidation reactions that utilize molecular oxygen as the sole oxidizing agent under environmentally benign conditions. This group has been exploring the activity of highly unsaturated ruthenium complexes with oxygen and nitrogen donor ligands for C-H bond activation reactions. The proposed research presents the detailed plans for studying C-H bond oxidation reactions mediated by novel bimetallic ruthenium-hydroxo complexes.Ihe second part of the proposed research focuses on the catalytic addition reactions of alkenes. In particular, metal-catalyzed conjugate addition of nitrogen and oxygen nucleophiles has been shown to be an effective method for forming a wide variety of biologically important beta-amino acids and -alkoxy ketones. Another reaction of current interest is the asymmetric hydrovinylation of alkenes, which has been shown to be a versatile method for forming new C-C bonds. The proposed research focuses on the development of highly effective chiral ruthenium catalysts for asymmetric conjugate addition of alcohols and hydrovinylation of alkenes. The detailed plans for examining the mechanisms of these reactions are also presented.The proposed research employs well-defined ruthenium-hydroxo and -amido complexes to effect catalytic C-H bond oxidation, conjugate addition of alcohols and hydrovinylation of alkenes. The proposed research seeks for both fundamental mechanistic understandings and the development of effective ruthenium catalysts for asymmetric conjugate addition of alcohols and hydrovinylation of alkenes.

描述(申请人提供)：过渡金属催化的非活性碳氢键的选择性氧化是一种直接的方法，或在温和的条件下由碳氢化合物生成醇和羰基化合物。受自然界中金属酶显著催化活性的启发，人们一直致力于开发实用的C-H键氧化反应的催化方法，在环境友好的条件下，利用分子氧作为唯一的氧化剂。该小组一直在探索高度不饱和的Ru与氧和氮供体配体的络合物对C-H键活化反应的活性。本研究提出了研究新型双金属Ru-羟基配合物催化C-H键氧化反应的详细计划。第二部分研究重点是烯烃的催化加成反应。特别是，金属催化的氮和氧亲核试剂的共轭加成反应已经被证明是一种有效的方法来生成各种具有重要生物学意义的β-氨基酸和-烷氧基酮。另一个当前感兴趣的反应是烯烃的不对称氢乙烯基化反应，这已被证明是形成新的C-C键的一种通用方法。这项研究的重点是开发高效的手性Ru催化剂，用于醇的不对称共轭加成和烯烃的氢乙烯基化反应。我们还提出了研究这些反应机理的详细计划。建议的研究使用定义明确的Ru-羟基和-氨基配合物来催化C-H键氧化、醇的共轭加成和烯烃的氢乙烯基化。这项研究既是为了了解基本的机理，也是为了开发有效的Ru催化剂，用于醇的不对称共轭加成和烯烃的氢乙烯基化。