1990 Fiscal Year Final Research Report Summary
Development of Catalytic Oxidation of Organonitrogen Compounds and Its Application to Organic Syntheses.
| Project/Area Number |
63850178
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B).
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
MURAHASI Shun-Ichi Osaka Univ. Faculty of Eng. Sci., Professor, 基礎工学部, 教授 (60029436)
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| Co-Investigator(Kenkyū-buntansha) |
INUI Shiro Mitsubishi Uka, Researcher, 研究員
IMADA Yasushi Osaka Univ. Faculty of Eng. Sci., Assistant, 基礎工学部, 助手 (60183191)
NAOTA Takeshi Osaka Univ. Faculty of Eng. Sci., Assistant, 基礎工学部, 助手 (20164113)
HOSOKAWA Takahiro Osaka Univ. Faculty of Eng. Sci., Assistant Prof., 基礎工学部, 助教授 (90029520)
IMADA Yasushi Osaka Univ. Faculty of Eng. Sci., Assistant (60183191)
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| Project Period (FY) |
1988 – 1990
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| Keywords | Amines / Sodium Tangstate / Nitrones / Hydroxamic acids / N-hydroxyamino Acids / Ruthenium Catalysts / Aminoalcohols / Lactams |
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| Research Abstract |
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.
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