| Project/Area Number |
61470091
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| Research Category |
Grant-in-Aid for General 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 | Hokkaido University |
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Principal Investigator |
SUGINOME Hiroshi Fac. of Engineering, Hokkaido University, 工学部, 教授 (00000779)
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| Co-Investigator(Kenkyū-buntansha) |
KOBAYASHI Kazuhiro Fac. of Engineering, Hokkaido University, 工学部, 助手 (90161976)
ORITO Kazuhiko Fac. of Engineering, Hokkaido University, 工学部, 助手 (20109482)
TOKUDA Masao Fac. of Engineering, Hokkaido University, 工学部, 助教授 (80001296)
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| Project Period (FY) |
1986 – 1987
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥6,300,000 (Direct Cost: ¥6,300,000)
Fiscal Year 1987: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1986: ¥5,200,000 (Direct Cost: ¥5,200,000)
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| Keywords | photochemical reactions / electro-organic synthesis / steroids / alkoxyl radicals / -scission / photo-rearrangements / macrocyclic ketones / 大環状ケトン / 分子内光転位反応 / アルコキシルラジカル / ピロリジン合成 / 有機合成 / ラジカル反応 / 転位反応 / 分子変換 |
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| Research Abstract |
1. A conformational dependence of [1,3] sigmatropic photo-rearrangements in , -unsaturated ketones was found by the study of the photolysis of two steroidal 7-membered , -unsaturated ketones.
2. The two new stereospecific rearrangements of excited steroidal oximes were found and mechanisms, which accommodate the stereospecificity of these photo-rearrangements proved by deuterium labelling studies, were proposed.
3. New mothed was devised for two carbon ring expansions of 5- and 6-membered rings of -indanone and - tetralone through the [2+2] photocycloaddition of the enol ethers of the cyclic ketones followed by the radical cleavage of the fused bond of benzohomotropones through [2+2] photocycloaddition of 1- and 2-naphthols with methyl acrylate followed by a -scission of alkoxyl radicals derived from the adducts was also achieved.
4. The photochemistries of cyclic -nitro ketones, 6-membered cyclic , '-dinitro ketones, and cyclic -nitro enones were studied and new photochemical processes of nitro compounds were found.
5. New method was devised on the synthesis of several furanocoumarins and furano quinolones based on the [2+2] photocycloaddition- -scission sequence.
6. Stereo-and regioselective synthesis of cis-1-alky1-2,5-disubstituted pyrrolidines by cyclization of aminyl radicals generated by anodic oxidation of lithium alkenylamides was devised.
7. A simple new general synthesis of marocyclic ketones based on a three-carbon annelation of cyclic ketones followed by the regioselective radical cleavage of the fused bond of the resulting bicyclic systems was devised. New synthesis of 15-membered cyclic ketones, exaltone and ( )-muscone, were achieved by this method.
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