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Development of Catalytic Oxidation of Organonitrogen Compounds and Its Application to Organic Syntheses.

有机氮化合物催化氧化的进展及其在有机合成中的应用。

基本信息

批准号：
63850178
负责人：
MURAHASI Shun-Ichi
金额：
$ 11.65万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B).
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1990
项目状态：
已结题

项目摘要

Transformation of organonitrogen compounds being contained in coal and oil-sand into useful material has attracted much attention in the field of industrial organic chemistry. In this study we thus aimed at developing clean, catalytic oxidation of organonitrogen compounds with metal-complex catalysts. Noteworthy are the following results.(1) Oxidation of secondary amines into nitrones undergoes smoothly, with SeO_2 catalyst as well as Na_2WO_4 is used with 30% aqueous hydrogen peroxide. Tetrahydroquinolines are converted into hydroxamic acids of potent antibacterial activity in excellent yields.(2) The oxidation developed in this study provides new and general strategy for the substitution at the alpha-position of secondary amines upon treatment of nitrones with various nucleophiles. For instance, simple, efficient, and inexpensive method for synthesis of amino acids from secondary amines has been established. Thus, catalytic oxidation of secondary amines with hydrogen peroxide followed by treatment with hydrogen cyanide gives alpha-cyanohydroxyl amines. Hydrolysis of the hydroxyl amines affords N-hydroxyamino acids which undergo catalytic hydrogenation to give amino acids. Treatment of nitrones with optically active enolates also gives beta-hydroxyamino acid esters in high diastereoselectivity.(3) In view of direct activation of C-H bonds adjacent to nitrogen of amines we have developed ruthenium-catalyzed oxidation of tertiary amines with tert-butyl hydroperoxide to give the corresponding alpha- (tert-butyldioxy) alkylamines. Selective N-demethylation of tertiary methyl amines is performed by the oxidation followed by acid catalyzed hydrolysis.(4) Intramolecular dehydrogenation of amino alcohols with RuH_2(PPh_3)_4 has been found to proceed smoothly when acetone is used as a hydrogen acceptor. Various lactams can be thus obtained by this method.

将煤和油砂中的有机氮化合物转化为有用物质在工业有机化学领域引起了极大的关注。因此，在本研究中，我们的目标是开发金属络合物催化剂对有机氮化合物的清洁催化氧化。值得注意的是：(1)仲胺在SeO_2催化剂和Na_2WO_4-30%过氧化氢水溶液中的氧化反应顺利进行。四氢喹啉以极高的产率转化为具有很强抗菌活性的异羟肟酸。(2)本研究开发的氧化反应为硝酮与各种亲核试剂处理时仲胺的α-位取代提供了新的一般策略。例如，已经建立了从仲胺合成氨基酸的简单、高效和廉价的方法。因此，用过氧化氢催化氧化仲胺，然后用氰化氢处理得到α-氰基羟胺。羟胺的水解制得N-羟基氨基酸，N-羟基氨基酸经催化氢化得到氨基酸。用光学活性的烯醇酸盐处理硝酮也得到了具有高非对映选择性的β-羟基氨基酸酯。(3)鉴于胺的氮附近的C-H键被直接激活，我们发展了Ru催化叔胺与叔丁基过氧化氢的氧化反应，得到了相应的α-(叔丁基二氧基)烷基胺。叔甲胺的选择性N-脱甲基反应是先氧化后酸催化的。(4)以丙酮为氢受体时，RuH_2(PPh_3)_4催化氨基醇的分子内脱氢反应顺利进行。用这种方法可以得到多种内酰胺类药物。