A Cyclochiral Conformational Motif Constructed Using a Robust Hydrogen-Bonding Network

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• 作者：Kenji Mishiro ; Takumi Furuta ; Takahiro Sasamori ; Kazuhiro Hayashi ; Norihiro Tokitoh ; Shiroh Futaki ; Takeo Kawabata
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：September 18, 2013
• 年：2013
• 卷：135
• 期：37
• 页码：13644-13647
• 全文大小：316K
• 年卷期：v.135,no.37(September 18, 2013)
• ISSN：1520-5126

文摘

A novel conformational motif constructed with a robust intramolecular hydrogen-bonding (H-bonding) network was discovered. A pyrrolidine derivative possessing four identical amide substituents at C(2) and C(5) formed a strong intramolecular H-bonding network consisting of all the amide groups. This conformation yielded a cyclochiral structure with a handedness that depended on the directionality of the H-bonding network. The most stable compound was isolated and applied to the acylative kinetic resolution of secondary alcohol. The handedness of the H-bonding network was biased by the presence of chiral substituents, and the preferred direction could be switched under an external stimulus. A structural analysis using NMR, X-ray crystallography, and theoretical calculation techniques indicated that the conformation of the substituents was highly ordered and depended on the directionality of the H-bonding network.