| Project/Area Number |
09640706
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | University of Tsukuba |
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Principal Investigator |
HOJO Makoto University of Tsukuba, Associate Professor, 化学系, 助教授 (50229150)
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| Co-Investigator(Kenkyū-buntansha) |
HOSOMI Akira University of Tsukuba, Professor, 化学系, 教授 (00004440)
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| Project Period (FY) |
1997 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 1998: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1997: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | manganese / chromium / ate complex / thiomethyl / allyl / propargyl / enolate / チオメチルアニオン / メタル化 / カルボニルイリド / [3+2]環化付加 |
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| Research Abstract |
Among transition metal ate complexes, the organocuprates have been predominantly investigated and utilized in organic synthesis, and reactions using these species are mainly based on their alkylating abilities. The reduction rarely takes place as a side reaction in these alkylations. This reductive nature of cuprates has been utilized for the direct generation of organocopper reagents in the cases where only a reductive process occurs. The organomanganese reagents were also reported to be alkylating agents. We found the generation of the enolates from the carbonyl compounds bearing a leaving group such as an acetoxy, siloxy, or halogen group at the a position by using the organomanganese(II) ate complexes and their characteristic reactions with electrophiles. From allyl and propargyl bromides, allyl- and propargylmanganese reagents were generated, and the direct generation of thiomethylmanganese reagents was also attained by the reaction of iodomethylsulfides and the manganese ate complex as a reductant. These reagents reacted with a variety of electrophiles. Chromium ate complexes also behaved as a reductant in the reaction of a-halo ketones and esters to generate chromium enolates that react with carbonyl compounds and alkyl halides efficiently. In the reactions with allyl or propargyl phosphates, the corresponding chromium reagents could be obtained.
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