Remarkable effects of chirality on deslipping reactions of diastereomeric rotaxanes and relevant mechanism involving pre-equilibrium.
The first clear differentiation on deslipping rates affected by the difference in the diastereomeric stereocenters of rotaxanes up to 8.4 times and unexpectedly large steric kinetic isotope effect on the deslipping reaction (ca. 20%) were observed. On the basis of the kinetic parameters, steric kinetic isotope effect, and (1)H NMR spectra of the nondeuteriated and deuteriated rotaxanes, we propose a deslipping mechanism involving pre-equilibrium.
Hirose
Keiji
K
Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 563-8531, Japan. hirose@chem.es.osaka-u.ac.jp
Nakamura
Yamato
Y
Tobe
Yoshito
Y
D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D043862:Rotaxanes / Q000737:chemistry*; D013237:Stereoisomerism
D043862:Rotaxanes