| Project/Area Number |
03453102
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | Osaka University |
|---|
Principal Investigator |
MATSUDA Haruo Osaka University, Faculty of Engineering, Professor, 工学部, 教授 (20028963)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
SHIBATA Ikuya Osaka University, Faculty of Engineering, Assistant Professor, 工学部, 助手 (10196420)
BABA Akio Osaka University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (20144438)
|
|---|
| Project Period (FY) |
1991 – 1992
|
| Project Status |
Completed (Fiscal Year 1992)
|
| Budget Amount *help |
¥6,900,000 (Direct Cost: ¥6,900,000)
Fiscal Year 1992: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1991: ¥4,900,000 (Direct Cost: ¥4,900,000)
|
|---|
| Keywords | Tin Enolate / Higher coordination / 1,4-Diketone / Tin Hydride / Stereoselective Reduction / 1.4-ジケトン / 官能基選択性 / スズエノラ-ト / ジアリルスズ / 有機スズ錯体 / 1.4ージケトン / アリルオキシラン / エポキシケトン / αーハロケトン |
|---|
| Research Abstract |
This study deals with novel synthetic use of organotin enolates and organotin hydrides, in which complexation of tin compounds with Lewis bases played an important role.
1. The reaction of tin enolates with alpha-haloketones. Tin enolates have been reported to react with alpha-haloketones at the carbonyl group to afford halohydrins or oxirane ring. In contrast, We have found the addition of coordinating compounds such as phosphine oxides to this reaction system afforded complete reversed chemoselectivity. Namely, the coupling reaction of tin enolates with halide group of alpha-haloketones took place. The formation of higher coordinated tin enolates played an important role for this unusual reactivity. This higher order species were detected by NMR spectra. Moreover, in addition of chemoselectivity, recent study revealed that control of stereoselectivity was established by using presented higher coordinated tin species.
2. Reduction of alpha-alkoxyketones with higher coordinated tin hydrides. In contrast to the conventional use using radical method, tin hydrides was revealed to employ efficient hydride donors by complexation with Lewis bases. Namely, this higher coordinating method afforded syn-alkoxy alcohols stereoselectively in the reduction of alpha-alkoxyketones. These results could be explained in terms of Felkin model. Moreover, recently, we have also recognized the stereoselective reaction in the reaction of alpha,beta-Epoxyketones.
|
