Ruthenium Catalyzed Oxidation and Addition Reactions

描述（由申请人提供）：过渡金属催化非反应碳氢键的选择性氧化是在温和条件下从碳氢化合物生成醇和羰基化合物的直接方法。受到自然界中金属酶显著的催化活性的启发，在环境友好的条件下，广泛的研究集中在开发利用分子氧作为唯一氧化剂的C-H键氧化反应的实用催化方法上。该小组一直在探索高度不饱和钌配合物与氧和氮供体配体在C-H键激活反应中的活性。提出了研究新型双金属钌-羟基配合物介导的C-H键氧化反应的详细计划。第二部分的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已被证明是形成各种生物上重要的β -氨基酸和-烷氧酮的有效方法。目前人们感兴趣的另一个反应是烯烃的不对称加氢乙烯化反应，这已被证明是形成新的C-C键的一种通用方法。本课题的研究重点是开发用于醇类不对称共轭加成和烯烃加氢乙烯化反应的高效手性钌催化剂。还提出了研究这些反应机理的详细计划。本研究采用定义明确的钌-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加氢乙烯化。提出的研究寻求对醇的不对称共轭加成和烯烃的加氢乙烯化的基本机理理解和有效的钌催化剂的开发。

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.