1993 Fiscal Year Final Research Report Summary
Development of Selective Oxidation of Alkenes by Heterometallic Catalysts and Its Synthetic Application
| Project/Area Number |
04555206
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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 |
MURAHASHI Shun-Ichi Osaka University, Dept.Chem., Prof., 基礎工学部, 教授 (60029436)
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| Co-Investigator(Kenkyū-buntansha) |
ATAKA Kikuo Ube Industry, Ube Research Institute, Researcher, 宇部研究所(研究員), 課長
IMADA Yasushi Osaka University, Dept.Chem., Research Associate, 基礎工学部, 助手 (60183191)
NAOTA Takeshi Osaka University, Dept.Chem., Research Associate, 基礎工学部, 助手 (20164113)
HOSOKAWA Takahiro Osaka University, Dept.Chem., Associate Prof., 基礎工学部, 助教授 (90029520)
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| Project Period (FY) |
1992 – 1993
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| Keywords | Allylic Compounds / Aldehydes / Asymmetric Acetalization / 1beta-Methylcarbapenem / Isoxazolidines / Hydroxylation / Hydroxyketones |
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| Research Abstract |
Development of effective, catalytic reactions which are highly controlled in terms of regio-and stereoselectivity is certainly required in the field of synthetic chemistry. Access to this problem is provided by the aid of metal complex catalysts. From such a view point, we have aimed to develop stereo-and regioselective oxidations of alkenes by using heterometallic catalysts. The major results obtained in this study are as follows.
1. We have developed palladium(II)-catalyzed asymmetric acetalization of methacrylic derivatives bearing optically active 2-oxazolidinones, from which optically active 3-hydroxy-2-methylpropanal is obtainable in high enantiomer excess. The reaction can be performed in large scale, and the aldehyde obtained was found to serve as a useful building block for the synthesis of an azetizinone derivative of 1beta-methylcarbapenem precursor.
2. Treatment of N-allylamides and lactams with molecular oxygen in the presence of a heterometalic catalyst consisting of PdCl_2, CuCl, and hexamethylphosphoric triamide was found to produce the corresponding aldehydes regioselectively. On the other hand, when water is present in the reaction system, it gives the corresponding methyl ketones. There is so far no precedent for such a complete reversal of the regioselectivity in this type of oxidations.
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