A Cyclochiral Conformational Motif Constructed Using a Robust Hydrogen-Bonding Network Kenji Mishiro Takumi Furuta Takahiro Sasamori Kazuhiro Hayashi Norihiro Tokitoh Shiroh Futaki Takeo Kawabata 10.1021/ja407051k.s003 https://acs.figshare.com/articles/journal_contribution/A_Cyclochiral_Conformational_Motif_Constructed_Using_a_Robust_Hydrogen_Bonding_Network/2376001 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. 2013-09-18 00:00:00 amide substituents intramolecular cyclochiral structure amide groups Cyclochiral Conformational Motif Constructed conformation handednes chiral substituents NMR directionality calculation techniques