Supramolecular complexation and enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid with 4-aminoprolinol derivatives as chiral hydrogen-bonding templates.
The photochirogenesis of 2-anthracenecarboxylic acid (AC) complexed to a hydrogen-bonding template (TKS159) was investigated to obtain mechanistic information on how chirogenesis is achieved for the dimerization of AC. Complexation of AC to TKS159 leads to the shielding of one of the two surfaces of the prochiral AC molecule. The two diastereomeric AC-TKS complexes, i.e., re-AC-TKS and si-AC-TKS, were characterized by changes in the UV-vis, fluorescence, and circular dichroism spectra and excited-state lifetimes. The ee is not simply determined by the diastereomeric ratio of the re- and si-AC-TKS complexes but also depends on the relative lifetimes of the diastereomeric complexes. The relative population of the re and si complexes was calculated from the enantiomeric excess (ee) for the products, taking into account the relative lifetimes of the two complexes. These studies established a protocol that can be used to reveal the mechanism for photochirogenesis by investigating the ground state and the excited state behavior of supramolecular systems.
Kawanami
Yuko
Y
Department of Applied Chemistry and Center for Advanced Science and Innovation, Osaka University, 2-1 Yamadaoka, Suita 565-0871, Japan.
Pace
Tamara C S
TC
Mizoguchi
Jun-ichi
J
Yanagi
Toshiharu
T
Nishijima
Masaki
M
Mori
Tadashi
T
Wada
Takehiko
T
Bohne
Cornelia
C
Inoue
Yoshihisa
Y
D000588:Amines / Q000737:chemistry*; D000873:Anthracenes / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D003500:Cyclization; D019281:Dimerization; D006860:Hydrogen Bonding; D015394:Molecular Structure; D010777:Photochemistry; D011759:Pyrrolidines / Q000737:chemistry*; D013237:Stereoisomerism
D000588:Amines; D000873:Anthracenes; D002264:Carboxylic Acids; D011759:Pyrrolidines; C010509:prolinol; C107996:anthracene-1-carboxylic acid