Ruthenium Catalyzed Oxidation and Addition Reactions

描述（由申请人提供）：过渡金属催化的非反应性碳-氢键的选择性氧化是一种在温和条件下由烃形成醇和羰基化合物的直接方法。受自然界金属酶催化活性的启发，人们致力于在环境友好的条件下，以分子氧为唯一氧化剂的C-H键氧化反应的实用催化方法的研究。该小组一直在探索具有氧和氮供体配体的高度不饱和钌络合物用于C-H键活化反应的活性。本论文的第二部分主要研究了烯类化合物的催化加成反应。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一种有效的方法，用于形成多种生物学上重要的β-氨基酸和β-烷氧基酮。目前感兴趣的另一个反应是烯烃的不对称加氢乙烯基化，这已被证明是形成新的C-C键的通用方法。本论文的研究重点是开发高效的手性钌催化剂，用于醇的不对称共轭加成和烯烃的加氢乙烯化反应。本文还提出了研究这些反应机理的详细方案，即利用结构明确的季铵盐-羟基和-氨基配合物催化C-H键氧化、醇的共轭加成和烯烃的加氢乙烯化反应。该研究旨在寻求基本的机理理解和有效的钌催化剂的不对称共轭加成醇和烯烃的加氢乙烯化的发展。

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.