Anomeric effect revisited. CH/n hydrogen bond hypothesis
-
- Takahashi Osamu
- Department of Chemistry, Graduate School of Science, Hiroshima University
-
- Yamasaki Katsuyoshi
- Department of Chemistry, Graduate School of Science, Hiroshima University
-
- Kohno Yuji
- Department of Materials Science, Yokohama National University
-
- Ueda Kazuyoshi
- Department of Materials Science, Yokohama National University
-
- Suezawa Yuko
- Ministry of Education, Culture, Science, Technology, and Sports
-
- Nishio Motohiro
- The CHPI Institute
Bibliographic Information
- Other Title
-
- アノマー効果再訪。ＣＨ／ｎ水素結合による解釈
Abstract
Ab initio MO calculations were carried out, at the MP2/6-311++G(d,p)//MP2/6-311G(d,p) level, to investigate the conformational Gibbs energy of 2-substituted oxanes and 1,3-dioxanes (Z = OCH3, F, Cl, Br). It has been found that the Gibbs energy of axial conformers is smaller than that of corresponding equatorial conformers in every case. In the axial conformers, the interatomic distance between Z and an axial C-H separated by four covalent bonds has been found appreciably shorter than the van der Waals distance, suggesting the importance of 5-member CH/n hydrogen bonds. NBO charges of the relevant protons and carbons have been shown noticeably different. In view of these findings, the CH/n hydrogen bonding has been suggested to play an important part in stabilizing the axial conformers; this may be a cause of the anomeric effect.
Journal
-
- Abstracts of Symposium on Physical Organic Chemistry
-
Abstracts of Symposium on Physical Organic Chemistry 18 (0), 49-49, 2006
The Society of Physical Organic Chemistry, Japan
- Tweet
Keywords
Details 詳細情報について
-
- CRID
- 1390001205555351168
-
- NII Article ID
- 130004645146
-
- Text Lang
- ja
-
- Data Source
-
- JaLC
- CiNii Articles
-
- Abstract License Flag
- Disallowed