| Project/Area Number |
13650922
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | KYUSHU UNIVERSITY |
|---|
Principal Investigator |
OHSHITA Joji KYUSHU UNIVERSITY, Institute for Fundamental Research of Organic Chemistry, Associate Professor, 有機化学基礎研究センター, 助教授 (90201376)
|
|---|
| Project Period (FY) |
2001 – 2002
|
| Project Status |
Completed (Fiscal Year 2002)
|
| Budget Amount *help |
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2002: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2001: ¥1,900,000 (Direct Cost: ¥1,900,000)
|
|---|
| Keywords | Acylsilane / Silene / Cope rearrangement / Thermal isomerization / Enolate anion / 有機ケイ素化合物 / 有機リチウム / Cope転位 |
|---|
| Research Abstract |
To know the synthetic utilities of acylpolysilanes, three novel types of acylpolysilanes were prepared and their thermal isomerization was studied and found that they may be useful precursors for linear conjugated silenes, as summarized bellow. In addition, it was found that the reactions of silaenolates prepared from acylpolysilanes with benzophenone readily produced dioxasilacyclopentane derivatives in good yields. These results clearly indicate that the acylpolysilanes are useful for the preparation of novel silicon reactive species as well as that of cyclic organosilicon compounds.
1) It was found that the reactions of lithium silaenolates with phenyl-substituted acetylenes afforded acyl-(Z)-ethenyldisilane as the first example of α-functionalized acylpolysilanes. Acylethenyldisilanes thus obtained underwent unique isomerization at >100 degree C via 2-siladiene intermediates. This appears to be an important methodology to produce siladiene at rather low temperature.
2) Thermal isomerization of a bis(acyl)disilane involving a 2,3-disiladiene intermediate, leading to the formation of a 1,2-disilacyclobuene derivative was investigated
3) Thermal isomerization of compounds having two acyl groups linked by a cycloalkane bridge took place at >120 degree C to give the respective ring-enlarged products. This is the first observation of oxa-Cope rearrangement of silenes.
|
