Transformation of aromatic compounds utilizing ambiphilicity of silylene
| Project/Area Number |
25708004
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| Research Category |
Grant-in-Aid for Young Scientists (A)
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| Allocation Type | Partial Multi-year Fund |
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| Research Field |
Organic chemistry
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| Research Institution | Tohoku University |
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Principal Investigator |
Ishida Shintaro 東北大学, 理学(系)研究科(研究院), 准教授 (90436080)
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| Project Period (FY) |
2013-04-01 – 2017-03-31
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| Project Status |
Completed (Fiscal Year 2016)
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| Budget Amount *help |
¥26,000,000 (Direct Cost: ¥20,000,000、Indirect Cost: ¥6,000,000)
Fiscal Year 2016: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2015: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2014: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2013: ¥11,830,000 (Direct Cost: ¥9,100,000、Indirect Cost: ¥2,730,000)
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| Keywords | シリレン / 脱芳香族化反応 / 環化付加反応 / ピリジン / ラジカル / 環化付加 / 高歪み化合物 / フラーレン / 複素環 / 速度論的安定化 / 低配位ケイ素化合物 / 含ケイ素環状化合物 / 脱芳香族化 / イリド / 酸化還元特性 / 歪みエネルギー |
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| Outline of Final Research Achievements |
(1) Regioselective photochemical cycloadditions of silylene with azulene and guaiazulene gave bicyclic [4]dendralene and heptafulvene derivatives, respectively. A red-shifted absorption band of thus obtained [4]dendralene was observed, which is attributed to the orbital interactions between dendralene and a silacyclopropane moieties. (2) Thermal dearomative cycloaddition of silylene with pyridines to afford azasilepins was investigated. (3) We found a silanol-catalyzed formal C-H insertion of silylene with pyridine. This reaction proceeds via deprotonation of silanol by base-coordinated silylene. (4) Phosphenium cation and silylene are isolobal. Thus, we planned oxidation of phosphinyl radical to synthesize phosphenium cation for the dearomative cycloaddition. We obtained phosphaalkene-silver complex by the oxidation of phosphinyl radical with silver salts. We succeeded in the generation of dicoordinate antimony- and bismuth-centered radicals as persistent species.
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Report
(5 results)
Research Products
(44 results)
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[Journal Article] A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene2016
Author(s)
Ohsato, T.; Okuno, Y.; Ishida, S.; Iwamoto, T.; Lee, K.-H.; Lin, Z.; Yamashita, M.; Nozaki, K.
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Journal Title
Angew. Chem. Int. Ed.
Volume: 55
Issue: 38
Pages: 11426-11430
DOI
Related Report
Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
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[Journal Article] Near-IR Absorbing Nickel(II) Porphyrinoids Prepared by Regioselective Insertion of Silylenes into Antiaromatic Nickel(II) Norcorrole2014
Author(s)
Takaki Fukuoka, Kenya Uchida, Young Mo Sung, Ji-Young Shin, Shintaro Ishida, Dr. Jong Min Lim, Satoru Hiroto, Ko Furukawa, Dongho Kim, Takeaki Iwamoto, Hiroshi Shinokubo
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Journal Title
Angewandte Chemie, International Edition
Volume: 53
Issue: 6
Pages: 1506-1509
DOI
Related Report
Peer Reviewed / Acknowledgement Compliant
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