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