1986 Fiscal Year Final Research Report Summary
Novel Type of Catalytic Oxidations of Oxygen- and Nitrogen-Containing Organic Compounds
| Project/Area Number |
60470095
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| Research Category |
Grant-in-Aid for General 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 |
MURAHASHI Shun-Ichi Faculty of Engineering Science, Osaka University, 基礎工学部, 教授 (60029436)
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| Co-Investigator(Kenkyū-buntansha) |
IMADA Yasushi Faculty of Engineering Science, Osaka University, 基礎工学部, 助手 (60183191)
NAOTA Takeshi Faculty of Engineering Science, Osaka University, 基礎工学部, 助手 (20164113)
HOSOKAWA Takahiro Faculty of Engineering Science, Osaka University, 基礎工学部, 講師 (90029520)
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| Project Period (FY) |
1985 – 1986
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| Keywords | Ruthenium catalyst / Hydroxylamine / Nitrone / Imine / Polyester / Cyanohydrin / アシルシアニド |
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| Research Abstract |
In view of that amines and alcohols are readily dehydrogenated by transition metal complexes such as palladium and ruthenium to give metal hydride intermediates, novel types of catalytic oxidations of these compounds were developed. Typical results are summarized below.
1. The catalytic oxidation of amines by hydrogen peroxide in the presence of sodium tungstate or selenium dioxide as the catalyst has proved to be a useful method for preparing the corresponding nitrones. This method has been also found to be useful for converting 1,2,3,4-tetrahydroquinolines into hydroxamic acids. Since nitrones are easily transformed into <alpha> -substituted hydroxylamines with various nucleophiles, the total synthesis of biologically active nitrogencontaining molecules, e.g. ochotensine, via nitrones has been investigated. During the course of this study hydroxylamines were found to be easily transformed into either amines or imines, depending on the reaction conditions chosen, by the use of titanium
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trichloride. The catalytic oxidation of secondary amines by tertbutyl hydroperoxide in the presence of ruthenium complexes as the catalyst has also proved to be a useful method for synthesizing imines.
2. The ruthenium-catalyzed oxidation of alcohols provides esters via dehydrogenation processes. From the viewpoint of practical use of the reaction, some esters of essential components in perfumes were prepared starting from alcohols, and polyesters from diols. Since the ruthenium-catalyzed oxidation of alcohols produces hydrogen molecule during the course of the reaction, it has been demonstrated that olefins is able to be hydrogenated in the same reaction medium. The ruthenium-catalyzed oxidation of cyanohydrins with tert-butyl hydroperoxide leading to acyl cyanides was developed. The acyl cyanides thus obtained were found to be utilized as chemoselective acylating reagents of primary amino group of polyamines. A short-step synthesis of naturally occurring polyamines such as spermine and spermidine alkaloids has been established by using this method. Less
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