title: Inherently chiral molecular clips: synthesis, chiroptical properties, and application to chiral discrimination.
abstract: Inherently chiral molecular clips (MCs), pseudoenantiomeric anti-1 and anti-2, as well as mesoid syn-3, were synthesized by diastereodifferentiating repetitive Diels-Alder reactions of the achiral bisdienophile 6 with chiral diene 5 generated in situ from (-)-menthyl 3,4-bis(dibromomethyl)benzoate 4. These MCs were successfully separated by chiral HPLC to give optically active anti-1 and anti-2 and almost optically inactive syn-3. The structures of anti-1, anti-2, and syn-3 were assigned by high-resolution NMR and the absolute configurations of anti-1 and anti-2 were determined by the exciton-chirality method. Optically active anti-2 can serve as a chiral host. It binds the HCl adduct of D-tryptophan methyl ester (D-TrpOMeHCl) 3.5 times stronger than the L-enantiomer (KD/KL=3.5).
authors.affiliation: ICORP Entropy Control Project, Department of Applied Chemistry, Osaka University, 2-1 Yamada-oka, Suita 565-0871, Japan.
authors.forename: Gaku
authors.initials: G
authors.lastname: Fukuhara
authors.forename: Süreyya
authors.initials: S
authors.lastname: Madenci
authors.forename: Jolanta
authors.initials: J
authors.lastname: Polkowska
authors.forename: Frank
authors.initials: F
authors.lastname: Bastkowski
authors.forename: Frank-Gerrit
authors.initials: FG
authors.lastname: Klärner
authors.forename: Yumi
authors.initials: Y
authors.lastname: Origane
authors.forename: Masayuki
authors.initials: M
authors.lastname: Kaneda
authors.forename: Tadashi
authors.initials: T
authors.lastname: Mori
authors.forename: Takehiko
authors.initials: T
authors.lastname: Wada
authors.forename: Yoshihisa
authors.initials: Y
authors.lastname: Inoue