Formation of Radical from Photoinduced Electron Transfer Reaction and its Application for Organic Synthesis
| Project/Area Number |
11640535
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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 |
Organic chemistry
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| Research Institution | Shimane University |
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Principal Investigator |
TAKUWA Akio Shimane university, Fac. Sci & Eng., Professor, 総合理工学部, 教授 (70032456)
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| Co-Investigator(Kenkyū-buntansha) |
IWAMOTO Hidetoshi Shimane university, Fac. Sci & Eng., Assistant Professor, 総合理工学部, 助教授 (00032623)
NISHIGAICHI Yutaka Shimane university, Fac. Sci & Eng., Assistant professor, 総合理工学部, 助教授 (00212118)
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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 |
¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2000: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
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| Keywords | 1, 2-diketone / allylsilane / allylstannane / 1, 2-naphthoquinone / allylation / allylic radical / photoinduced electron transfer / α-ジケトン / 14族金属複合試薬 / フリル化反応 / 光付加反応 / アリシラン / 光電子移動 / アリル化反応 |
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| Research Abstract |
In this research project, we found the following regio-and stereo-selective synthesis using radical species produced by photoinduced single electron transfer (SET) reactions.
1. Irradiation of a CH_3CN solution of a-diketones and allylsilane/allylstannane-bifunctional reagent which possesses both allylic silane and allylic stannane functionality in the same molecule sharing the same carbon-carbon double bond afforded α-ketohomoallyl alcohol having allylsilane moiety in good yields. These results indicate that the (alkyl) C-Sn bond rather than (alkyl) C-Si bond of the cation radial formed by photoinduced SET reaction of the bifunctional reagent cleavages selectively to give allylic radical having allylsilane moiety, and the resulting allylic radical couples with semidione radical to form the α-ketohomoallyl alcohol. When the treatment of the irradiated mixture with Mg(CO_4)_2 cis-methylenecyclopentane-1, 2-diols were obtained, whereas the treatment with tetrabutylammonium fluoride (TBAF) yielded trans-1, 2-diols.
2. 1, 2-Naphthoquinone reacted with γ-substituted allyltin reagents in both thermal and photochemical conditions to yield 4-allyl-1, 2-naphthoquinone. The opposite regioselectivity of introduced allylic moiety was observed in both reaction conditions.
3. The photochemical reaction of 1, 2-naphthoquinones with allylsilanes afforded [3+2] cycloadducts via diradical intermediate, which was converted to 3-allyl-1, 2-naphthoquinones in moderate to good overall yields by treatment with boron trifluoride, ammonium cerium nitrate or TBAF.
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Report
(3 results)
Research Products
(9 results)
