|
インデックス |
|
Permalink : http://id.nii.ac.jp/1094/00002550/
Stereoselectivity and vertical polarity hypothesis for carbonyl addition
利用統計を見る
| File / Name | License |
|---|---|
| uchiyama_carbonyl_2019 |
|
uchiyama_carbonyl_2019
(717.58KB)
|
|
|
オープンアクセス
|
|
 |
 |
 |
 |
 |
| アイテムタイプ | 紀要論文 / Departmental Bulletin Paper |
|---|---|
| 言語 | 英語 |
| キーワード |
theoretical hypothesis, carbonyl, transition state of boat form, steric effect, valence shell electron pair repulsion theory, 4-t-butylcyclohexanone, lithium aluminum hydride, 1,4-flagpole interaction, Cram's rule |
| 著者 |
内山 文昭
/ ウチヤマ フミアキ
( CiNii ID: 9000317568295 ) |
| 著者別名 |
Uchiyama Fumiaki
( CiNii ID: 9000333926818 ) |
| 抄録 |
The polarity of π bond of carbonyl groups always occurs horizontally to carbonyl plane. This polarity is used as “horizontal polarity” in this paper. The horizontal polarity determines the reactivity to nucleophilic addition of carbonyl groups and is indicated as LUMO in molecular orbital method. I assume that the vertical shift of π electron density of carbonyl groups, named“vertical polarity”, occurs perpendicular to the plane of carbonyl groups by electron repulsion under the constant geometry of carbonyl atoms. The π electorn density in the vertical polarity changes perpendicular to the plane of carbonyl molecules. I propose that the big lobe caused by the vertical polarity stabilizes the overlapping with the nucleophilic electron pair in the transition state and determines the stereoselectivity in the nucleophilic addition of carbonyl groups. I show that the concept of the vertical polarity is verified from the stereoselective reduction of 4-t-butylcyclohexanone and the chiral induction at acyclic carbonyl carbons during nucleophilic additions.
|
| 雑誌名 | 中村学園大学薬膳科学研究所研究紀要 |
| 号 | 11 |
| ページ | 1 - 5 |
| 発行年 | 2019-03 |
| 出版者 |
中村学園大学薬膳科学研究所
|
| ISSN |
1882-9384
|
