TY - JOUR
T1 - Manipulating γ-cyclodextrin-mediated photocyclodimerization of anthracenecarboxylate by wavelength, temperature, solvent and host
AU - Yang, Cheng
AU - Wang, Qian
AU - Yamauchi, Masahito
AU - Yao, Jabing
AU - Zhou, Dayang
AU - Nishijima, Masaki
AU - Fukuhara, Gaku
AU - Mori, Tadashi
AU - Liu, Yu
AU - Inoue, Yoshihisa
PY - 2014/2
Y1 - 2014/2
N2 - Wavelength effects on the enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate (AC) mediated by native and modified γ-cyclodextrins (CDs) were examined in different solvents at varying temperatures to manipulate the photochirogenic outcomes beyond the thermodynamically determined re/si-enantiotopic face selectivity upon 2:1 complexation of AC with CD in the ground state. Indeed, the stereochemical outcomes, i.e. syn/anti, head-to-tail/head-to-head (HT/HH) and in particular enantiomer ratios, were critical functions of the irradiation wavelength, irrespective of the CD host employed. Furthermore, the wavelength effects observed strongly depended on the host structure, reaction temperature and solvent employed, for which altered stacking geometry of the complexed AC pair is thought to be responsible. By optimizing the irradiation wavelength, chiral host, temperature and solvent, an enantiomeric excess of up to 54 and -37% were achieved for chiral syn-HT and anti-HH dimers.
AB - Wavelength effects on the enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate (AC) mediated by native and modified γ-cyclodextrins (CDs) were examined in different solvents at varying temperatures to manipulate the photochirogenic outcomes beyond the thermodynamically determined re/si-enantiotopic face selectivity upon 2:1 complexation of AC with CD in the ground state. Indeed, the stereochemical outcomes, i.e. syn/anti, head-to-tail/head-to-head (HT/HH) and in particular enantiomer ratios, were critical functions of the irradiation wavelength, irrespective of the CD host employed. Furthermore, the wavelength effects observed strongly depended on the host structure, reaction temperature and solvent employed, for which altered stacking geometry of the complexed AC pair is thought to be responsible. By optimizing the irradiation wavelength, chiral host, temperature and solvent, an enantiomeric excess of up to 54 and -37% were achieved for chiral syn-HT and anti-HH dimers.
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U2 - 10.1039/c3pp50255d
DO - 10.1039/c3pp50255d
M3 - Article
C2 - 24057104
AN - SCOPUS:84893133610
VL - 13
SP - 190
EP - 198
JO - Photochemical and Photobiological Sciences
JF - Photochemical and Photobiological Sciences
SN - 1474-905X
IS - 2
ER -