| Project/Area Number |
05555246
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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 | Nagasaki University |
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Principal Investigator |
TAMARU Yoshinao Nagasaki University Fac.of Engineering Professor, 工学部, 教授 (80026319)
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| Co-Investigator(Kenkyū-buntansha) |
NISI Seiichi Ajinomoto CO.LTD.Researcher, 東海工場技術部, 研究員
TANAKA Shuji Nagasaki University Fac.of Engineering Associate Professor, 工学部, 助教授 (80217033)
普神 敬悟 長崎大学, 工学部, 助手 (90202283)
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| Project Period (FY) |
1993 – 1995
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| Project Status |
Completed (Fiscal Year 1995)
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| Budget Amount *help |
¥15,100,000 (Direct Cost: ¥15,100,000)
Fiscal Year 1995: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1994: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1993: ¥7,000,000 (Direct Cost: ¥7,000,000)
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| Keywords | Aminocarbonylation / Palladium Catalysis / Carbon monoxide / Chemoselectivity / Carbamate (endo-, exo-) / Urea / ジエニルアミノ化 / 一酸化炭素 / アリルアミン |
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| Research Abstract |
exo-Ureas, endo-ureas, exo-sulfonamides, and exo-carbamates readily undergo aminocarbonylation by the catalysis of PdC12 in methanol under 1 atm of carbon monoxide at room temperature. O-Allyl-endo-carbamates, on the other hand, do not undergo the aminocarbonylation under the similar conditions. This makes sharp contrast to the fact that endo-ureas are more reactive toward aminocarbonylation than exo-ureas. After experimentations, we found that aminocarbonylation of endo-carbamates proceed smoothly in the presence of sodium acetate and methyl orthoacetate (MOA). MOA can be utilized as an additive (in MeOH as a solvent) or as a solvent. In the latter case, MOA serves not only as a solvent but also as a reactant (a nucleophile) and much higher stereoselectivities are observed then the case undertaken in MOA/MeOH.Diamines possessing endo-carbamate and exo-carbamate (exo-urea or exo-sulfonamide) moieties in the same molecules were found to undergo chemoselective amination : the endo-carbamate moieties in MOA and the exo-carbamate, exo-urea, and exo-sulfonamide moieties in MeOH undergo the selective aminocarbonylation under 1 atm of CO by the catalysis of PbC12.
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