| Project/Area Number |
11650881
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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 | Tohoku University |
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Principal Investigator |
INOUE Yoshio Tohoku University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (50005518)
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| Co-Investigator(Kenkyū-buntansha) |
OI Shuichi Tohoku University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (00241547)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2001: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2000: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1999: ¥1,300,000 (Direct Cost: ¥1,300,000)
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| Keywords | cationic platinum complex / enyne / sleletal reorganization / metathesis / vinylcyclopentene / cyclization / 白金錯体 / 1.6-エンイン / 1,6-エンイン / 骨核再構成反応 |
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| Research Abstract |
The skeletal reorganization of 1,6-enyne having a methyl group on the acetylene terminus was examined in CHCl_3 at room temperature for 20 h in the presence of 2 mol% of cationic platinum complexes. This reaction afforded the cyclized product having a methyl group on the terminal of the vinyl group. This reaction involves the cleavage of both the double and triple carbon-carbon bonds, which was confirmed by ^<13>C- and ^2H-labeling experiments. No ordinal rearranged product was observed by either GC-MS or NMR analysis. The effect of the various catalysts in this reaction has been examined. A series of cationic platinum (and palladium in certain cases) complexes coordinated with bidentate diphosphine ligands such as dppe, dppp, and dppb exhibited good catalytic activities, affording the unusual rearrangement product in approximately 75% yield. The Z isomer was obtained preferentially in the case of dppp and dppb. The complex coordinated with the monodentate ligand of PPh_3 exhibited only minor catalytic activity. Neither neutral dichloroplatinum complexes such as PtCl_2(dppp) and PtCl_2(PPh_3)_2 nor cationic palladium complexes such as [Pd(dppp)(PhCN)_2](BF_4)_2 and [Pd(PPh_3)_2(PhCN)_2](BF_4)_2 exhibited catalytic activity under the same reaction conditions. CHCl_3 and CH_2Cl_2 were suitable solvents for this cyclization, and no reaction occurred in other solvents such as THF, acetone, acetonitrile, and nitromethane. Reaction pathways involving the rearragement of homoallyl and cyclopropylcarbinyl cations were proposed based on these experimental results.
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