| Project/Area Number |
60840014
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Nagoya University |
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Principal Investigator |
NOYORI Ryoji Professor; Fuculty of Science, Nagoya University, 理学部, 教授 (50022554)
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| Project Period (FY) |
1985 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥5,500,000 (Direct Cost: ¥5,500,000)
Fiscal Year 1986: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1985: ¥3,500,000 (Direct Cost: ¥3,500,000)
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| Keywords | Enolates / TAS enolates / TAS phenoxide / TASエノラート / エリトロ選択性 / 非環状延伸型遷移状態 / 超カチオン / アルドール反応 / スーパーカチオン / 超反応剤 / トリス(ジアルキルアミノ)スルホニウム(TAS) / nakedness / アルキル化反応 / アシル化反応 |
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| Research Abstract |
<^1H> NMR indicates that a mixture of phenyl trimethylsilyl ether and tris(diethyl-amino) sulfonium (TAS) difluorotrimethylsiliconate in THF exists in a dynamic equilibrium with TAS phenoxide and fluorotrimethylsilane. Evacuation of the volatile fluorosilane gives TAS phenoxide as air-sensitive crystals. This is also the case with an enol trimethylsilyl ether of benzyl methyl ketone, allowing the preparation of the TAS enolate. The conductivity measurement and the <^1H> and <^(13)C> NMR study have revealed the ionic nature of the TAS phenoxide and enolate in THF. These species display unique stereo-, chemo-, and regioselectivities in the nucleophilic reactions.
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