Development of novel addition reactions based on the key concept of carbon-metal-hetero atom bonds
| Project/Area Number |
14550817
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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 | Gunma University |
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Principal Investigator |
FUGAMI Keigo Gunma University, Department of Chemistry, Research Associate, 工学部, 助手 (90202283)
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| Project Period (FY) |
2002 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2004: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2003: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥1,700,000 (Direct Cost: ¥1,700,000)
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| Keywords | Organotin Reagent / Organogermanium Reagent / Palladium Catalyst / Addition Reaction / Mizoroki-Heck Reaction / Carbostannylation Reaction / Hyoer-Valent Tin Compound / Heteroatom Compound / 有機ゲルマニウム / クロスカップリング反応 / 有機スズ / ハロゲン化物 / 熱分解 / アルケニルゲルマン / 置換反応 / 溝呂木-Heck-反応 / アトムエコノミー反応 / 環境調和型有機合成 / 高効率反応剤 |
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| Research Abstract |
The reporter has focused on compounds that possess carbon-tin-hetero atom-or carbon-germanium-heteroatom bonds from synthetic point of view. On the investigation, it was revealed that Lewis acidity tin and germanium with those bonds are enhanced. It resulted in discoveries of new aspects in organotin-and germanium chemistries as follows : 1.oxidative addition to palladium(0) species is facilitated ; 2.due to the enhancement of Lewis acidity of the resulting adduct realized otherwise sluggish carbopalladation process ; 3.tend to form a hyper-valent species, nucleophilicity of the carbon groups attached on tin or germanium are significantly enhanced upon addition of a proper anionic ligand.
Based on above mentioned discoveries, several synthetically useful new carbon-carbon bond-formation reactions could be developed. Especially, achievement of utilization of plural organic moieties attached to tin or germanium toward the cross-coupling reactions, that had been widely regarded practically impossible, is noteworthy.
The newly developed synthetic organic reactions are listed below :
1.Tetraaryltin-mediated novel Mizoroki-Heck-type reaction utilizing plural organic moieties attached to a tin atom.
2.Palladium-catalyzed cross-coupling reaction of tetraaryl-and -alkenyltin reagents that utilizes all four organo groups on tin.
3.Arylstannylation of norbornene.
4.Allylstannylation of norbornene.
5.Palladium-catalyzed oxidative 2;1 cyclocondensation of norbornene and 1-alkenyltin trichloride.
6.Aryltin trichloride-mediated Mizoroki-Heck reaction that does not require added oxidant.
7.Alkynylgermylation of norbornene and its derivatives.
8.New stereoselective synthesis of Z-enynylgermanium trichloride by means of thermal cracking of alkynylgermylated norbornadiene.
9.Novel palladium-catalyzed cross-coupling reaction of arylgermanium trichlorides.
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Report
(4 results)
Research Products
(22 results)
