| Project/Area Number |
08454230
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | Osaka Prefecture University |
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Principal Investigator |
MIZUNO Kazuhiko Osaka Prefecture University, College of Engineering, Professor, 工学部, 教授 (10109879)
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| Co-Investigator(Kenkyū-buntansha) |
MAEDA Hajime Osaka Prefecture University, College of Engineering, Research Associate, 工学部, 助手 (40295720)
MATSUMURA Noboru Osaka Prefecture University, College of Engineering, Research Associate, 工学部, 助手 (40125274)
SUGIMOTO Akira Osaka Prefecture University, College of Engineering, Associate Professor, 工学部, 助教授 (00081323)
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| Project Period (FY) |
1996 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥6,300,000 (Direct Cost: ¥6,300,000)
Fiscal Year 1997: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1996: ¥4,200,000 (Direct Cost: ¥4,200,000)
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| Keywords | Photoinduced Electron Transfer / Exciplex / Fluorescence Quenching / Photosensitizer / Photochemical Polar Addition / Photocycloaddition / Cage Compounds / Dipole Moment / 不斉光反応 / エナンチオ選択性 / ジアステレオ選択性 / (4+4)光環化付加体 / エナンチオマー / ラジカルイオン / 分子内光環化付加反応 |
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| Research Abstract |
The title subject was investigated and the following results were obtained :
1. Chiral discrimination is observed in the fluorescence quenching of S- (+) -and R- (-) -2,2'-dimethyl-1,1'-bianthryls (1a and 1b) by a variety of chiral quenchers. Quenching rates are varied depending on the structures, electron-donating abilities, and chiralities of the quenchers. The largest chiral discrimination is found in the fluorescence quenching of 1a by the enantiomer pair (+) -and (-) -N-(alpha-methylbenzyl) -2,5-dimethylpyrrole.
2. Chiral discrimination is also observed in the fluorescence quenching of emissive exciplexes generated from 1a and aromatic amines such as dimethylaniline (2) by chiral quenchers. The kqtau ratio in the fluorescence quenching of the exciplex emission of 1a/2 and 1b/2 systems by (+) -menthyl cinnamate in benzene shows a maximum value of 1.08, and is decreased with increasing polarity of solvents. These results indicate that the chiral quenchers interact with chiral exciplexes in a enantioselective manner.
3. Photochemical polar additions of alcohols to arylalkenes catalyzed by chiral sensitizers such as 1,4-dicyanonaphthalene and 9,10-dicyanoanthracene bearing menthyl and cholesteryl group are investigated. Anti-Markovnikov addition of methanol to 1,1-diphenylpropene sensitized by 2-cholesteryloxymethyl-1,4-dicyanonaphthalene shows a maximum value, a 27% enantiomeric excess.
4. Inter- and intramolecular photocycloadditions between furan and naphthalene derivatives having chiral alkoxycarbonyl group (s) at 1- or 2,3-position (s) of naphthalene ring give (4+4) cycloadducts and cage compounds in a diastereoselective manner, respectively. Moreover, it is revealed that the regiochemistry of products is governed by dipolar moments of exciplexes.
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