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

低价钌配合物催化反应的设计与开发

基本信息

批准号：
02403019
负责人：
MURAHASHI Shun-Ichi
金额：
$ 23.36万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1992
项目状态：
已结题

项目摘要

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

低价过渡金属络合物，尤其是Ru络合物，由于其具有多种氧化态(从Ru(-II)到Ru(VIII))和与氧、氮原子的配位能力而备受关注。对于低价Ru络合物催化剂，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)丁腈的C-H活化。1.Ru催化的叔丁基氢过氧化氢与三元N-甲胺的反应，高效地合成了相应的α-(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型机理进行的，其中氧-Ru(IV)是关键中间体。酰胺和内酰胺与过氧化氢的氧化也在温和的反应条件下进行，得到含氧产物。用过氧乙酸对β-内酰胺进行类似的处理可得到关键的中间体…S更多地用于合成碳青霉烯类抗生素。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，只要用等摩尔量的水处理，Ru催化的氰化物水合反应就能高效进行。对酰胺形成原理的扩展揭示了腈的新的催化转化。因此，在两个当量水的存在下，Ru催化的氰化物与胺的缩合反应伴随着氨的析出而得到相应的酰胺。各种工业上重要的聚酰胺的合成突显了本工艺的效率。通常情况下，在水存在下，Ru催化的二腈与二胺的反应生成聚酰胺。氨基腈可以有效地进行类似的缩聚反应。3.在温和和中性条件下，Ru催化的腈与羰基化合物的羟醛缩合反应。在相似的反应条件下，腈类化合物与含吸电子基团的烯烃反应生成相应的Michael加合物。本反应的一个重要特征是在其他活性亚甲基化合物存在的情况下，腈与羰基化合物或Michael受体发生化学选择性反应。较少