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

低价过渡金属配合物，特别是钌配合物引起了人们的兴趣，因为钌配合物具有多种氧化态（从Ru（-II）到Ru(VIII)），并且与氧原子和氮原子具有很强的配位能力。对于低价钌络合催化剂，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. 钌催化三元n -甲胺与过氧化叔丁基反应，高效生成相应的-（叔丁基二氧基）甲胺。动力学实验表明，该反应是通过细胞色素P-450型机制进行的，其中氧化钌（IV）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。用过氧乙酸对-内酰胺进行类似处理，可以得到-乙酰氧基- -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，碳氢化合物可以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，钌催化腈的水化效果非常好。酰胺形成原理的延伸揭示了腈的新型催化转化。因此，钌催化的腈与胺的缩合在两等量的水的存在下，随着氨的演化，得到相应的酰胺。通过合成各种工业上重要的聚酰胺，突出了本工艺的效率。钌催化二腈与二胺在水的存在下反应，通常得到聚酰胺。氨基腈进行类似的有效缩聚。3. 钌催化羰基化合物与腈的醛缩反应是在温和和中性条件下进行的。在类似的反应条件下，腈与带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在其它活性亚甲基化合物存在的情况下，腈与羰基化合物或迈克尔受体的化学选择性反应。少

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