Design and Development of Catalytic Reactions Promoted by Low Valent Ruthenium Complexes

低价过渡金属配合物，特别是钌配合物受到人们的关注，因为钌配合物具有多种氧化态（从Ru（-II）到Ru（VIII））以及与氧和氮原子的强配位能力。对于低价钌配合物催化剂，我们研究了三种类型的反应。 1)细胞色素P-450型氧化。 2)路易斯酸促进反应。 3）腈的C-H活化。 1. N-甲基叔胺与氢过氧化叔丁基在钌催化下反应，高效生成相应的α-(叔丁基二氧基)甲基胺。动力学实验表明该反应通过细胞色素P-450型机理进行，其中氧代钌(IV)物质作为关键中间体。酰胺和内酰胺与过氧化物的氧化也在温和的反应条件下进行，得到氧化产物。用过乙酸对 β-内酰胺进行类似处理，得到 β-乙酰氧基-β-内酰胺，这是合成碳青霉烯类抗生素的关键中间体。通过使用这些催化体系，可以对烃类进行直接氧化，得到相应的醇和酮。 2. 在中性条件下，仅用等摩尔量的水处理即可高效地进行钌催化的腈水合。酰胺形成原理的扩展揭示了腈的新型催化转化。因此，在两当量水存在下，钌催化的腈与胺的缩合反应生成相应的酰胺，同时放出氨。本方法的效率通过各种工业上重要的聚酰胺的合成得到凸显。通常，在水存在下，二腈与二胺的钌催化反应会生成聚酰胺。氨基腈可以有效地进行类似的缩聚反应。 3.钌催化的腈与羰基化合物的羟醛型缩合反应在温和中性条件下进行。在相似的反应条件下，腈与带有吸电子基团的烯烃反应生成相应的迈克尔加合物。本反应的一个重要特征是腈与羰基化合物或迈克尔受体在其他活性亚甲基化合物存在下的化学选择性反应。较少的

Low valent transition metal complexes,particularly ruthenium complexes are of interest,because ruthenium complexes have various oxidation states(from Ru(-II) to Ru(VIII))and strong coordination ability to oxygen and nitrogen atoms. Concerning to low valent ruthenium complex catalyst,we have investigated three type of reactions. 1)Cytochrome P-450 type oxidation. 2)Lewis acid promoted reaction. 3)C-H activation of nitrile. 1. Ruthenium-catalyzed reaction of teriary N-methylamines with t-butyl hydroperoxide gives the corresponding alpha-(t-butyldioxy)methylamines highly efficiently. The kinetic experiments indicate that the present reaction proceeds via Cytochrome P-450 type mechanism,which involves oxo-ruthenium(IV) species as a key intermediates. The oxidation of amides and lactams with peroxides also proceeds under mild reaction conditions to give the oxygenated products. Similar treatment of beta-lactams with peracetic acid affords beta-acetoxy-beta-lactams which are key intermediate … More s for the synthesis of carbapenem antibiotics. By using these catalytic systems,direct oxidation of hydrocarbons can be performed to give the corresponding alcohols and ketones. 2. Ruthenium-catalyzed hydration of nitriles proceeds highly efficiently upon treatment with only equimolar amount of water under neutral conditions. Extension of the principle of the amide formation disclosed novel catalytic transformations of nitriles. Thus,ruthenium-catalyzed condensation of nitriles with amines in the presence of two equivalents of water gives the corresponding amides along with evolution of ammonia. The efficiency of the present process is highlighted by the synthesis of various industrially important polyamides. The ruthenium-catalyzed reaction of dinitriles with diamines in the presence of water gives polyamides, generally. Aminonitriles undergo similar polycondensation efficiently. 3. The ruthenium-catalyzed aldol-type condensation of nitriles with carbonyl compounds proceeds under mild and neutral conditions. Under the similar reaction conditions,nitriles react with alkenes bearing electron withdrawing group to give the corresponding Michael adducts. One important feature of the present reactions is the chemoselective reaction of nitriles with carbonyl compounds or Michael acceptors in the presence of other active methylene compounds. Less