Theoretical calculation of electronic circular dichroism of the rotationally restricted 3,8"-biflavonoid morelloflavone

[Graphics] Theoretical calculation of electronic circular dichroism (ECD) of the rotationally restricted 3,8 ''-biflavonoid (+)-morelloflavone using time dependent density functional theory (TDDFT), performed at 298 K at B3LYP-SCRF/6-31G*/B3LYP/6-31G* level with COSMO model, permitted unequivocal assignment of its 2R,3S absolute configuration. The experimentally observed Cotton effect (CE) around 290 nm is contributed by the acetophenone pi -> pi* transition of the ABC-flavanone moiety and the electronic transition within the DEF-flavone moiety, while another diagnostic positive CE around 350 nm is attributable to the electronic interaction between the ABC-flavanone moiety and the DEF-flavone moiety, as well as the electronic transition within the DEF-flavone moiety. The remarkable differences of the calculated ECD of its two rotamers indicate that the rotational restrictions significantly affect the ECD of 3,8"-biflavonoids. Empirical ECD rules derived from monomeric flavonoids may not be applicable to configurational assignment of complex 3,8"-biflavonoids. This study has provided new insights in interpreting the experimentally observed ECD spectra of this class of compounds.