| Project/Area Number |
11650882
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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 |
Synthetic chemistry
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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) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Keywords | manganese / chromium / ate complex / iron / catalyst / thiomethyl / allyl / carbolithiation / カルボメタル化 / 有機亜鉛 / アルキルリチウム / 3置換アルケン / 分子内環化 |
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| Research Abstract |
In contrast to ate-complexes based on main-group elements, transition-metal ate complexes are expected to be reductants besides alkylating agents, since the ate-complexes, the electron-excess system may react with electrophiles through the oxidative addition. We planed to investigate the reductive behavior of the transition metal ate complexes and found the direct and reductive generation of organometallic reagents starting from several electrophiles.
Thus tributylmanganate reagent reacted with iodomethyl sulfides to produce the corresponding thiomethylmanganese reagents. In this reaction, metal-halogen exchange reaction proceeds rapidly even at-78℃, while the oxidative addition of iodomethyl sulfide to the manganese ate complex takes place predominantly at -20℃. Thiomethylmanganese reagents react with allyl bromides, enones, and aldehydes.
Chromium ate complexes also reduce allyl phosphates to generate allylchromium reagents. We also found iron-catalyzed carbolithiation of alkynes, where the regio-and stereochemically defined multi-substituted vinyllithium reagents were produced. In this reaction, ate-type complex based on low valent iron is thought to be an actual catalyst.
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