Carroll反応におけるジェミナル結合関与 / Geminal Bond Participation in the Carroll Rearrangement
- Resource Type
- Journal Article
- Authors
- Miyu SHIOMI; Yasuhiro TODO; Yuji NARUSE; 塩見 弥有; 成瀬 有二; 藤堂 泰裕
- Source
- Abstracts of Symposium on Physical Organic Chemistry. 2011, :2
- Subject
- Bond Model Analysis
Carroll Rearrangement
Carroll転位反応
Diastereoselectivity
Geminal Bond Participation
Interbond Energy
ジアステレオ選択性
ジェミナル結合関与
結合モデル解析
結合間エネルギー
- Language
- Japanese
We report here that the geminal bond participation in the Carroll rearrangement. The electronic structure at the transition state (TS)of the model reaction was subjected to the bond model analysis, which showed that the interaction to the geminal bond at the Z-position greatly stabilized the TS. Therefore, We can predict that the substituent with the more electron-donating sigma-bond should prefer to occupy the Z-position of the product. We designed the alkyl- and silyl-substituted substrates. The Z-selectivity was confirmed by the theoretical calculations and the experoments. Substitution of the silicon atom to a germanium should enhance the selectivity, which was also confirmed by the calculations and the experiments.