Inherently chiral molecular clips: synthesis, chiroptical properties, and application to chiral discrimination.
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).
Fukuhara
Gaku
G
ICORP Entropy Control Project, Department of Applied Chemistry, Osaka University, 2-1 Yamada-oka, Suita 565-0871, Japan.
Madenci
Süreyya
S
Polkowska
Jolanta
J
Bastkowski
Frank
F
Klärner
Frank-Gerrit
FG
Origane
Yumi
Y
Kaneda
Masayuki
M
Mori
Tadashi
T
Wada
Takehiko
T
Inoue
Yoshihisa
Y