title: A first-principles examination of the asymmetric induction model in the binap/Rh(I)-catalysed 1,4-addition of phenylboronic acid to cyclic enones by density functional theory calculations.
abstract: First-principles modelling of the diastereomeric transition states in the enantiodiscrimination stage of the catalytic cycle can reveal intimate details about the mechanism of enantioselection. This information can be invaluable for further improvement of the catalytic protocols by rational design. Herein, we present a density functional theory (IEFPCM/PBE0/DGDZVP level of theory) modelling of the carborhodation step for the asymmetric 1,4-arylation of cyclic α,β-unsaturated ketones mediated by a [(binap)Rh(I)] catalyst. The calculations completely support the older, qualitative, pictorial model predicting the sense of the asymmetric induction for both the chelating diphosphane (binap) and the more recent chiral diene (Phbod) ligands, while also permitting quantification of the enantiomeric excess (ee). The effect of dispersion interaction correction and basis sets has been also investigated. Dispersion-corrected functionals and solvation models significantly improve the predicted ee values.
authors.affiliation: Department of Pharmaceutical Engineering, School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Rd., Wuhan 430070 (P. R. China), Fax: (+86) 2787749379. qinhuali@whut.edu.cn.
authors.forename: Hua-Li
authors.initials: HL
authors.lastname: Qin
authors.forename: Xiao-Qing
authors.initials: XQ
authors.lastname: Chen
authors.forename: Yi-Zhen
authors.initials: YZ
authors.lastname: Huang
authors.forename: Eric Assen B
authors.initials: EA
authors.lastname: Kantchev
mesh_terms: D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D003512:Cyclohexanones / Q000737:chemistry*; D003517:Cyclopentanes / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008958:Models, Molecular; D010720:Phosphines / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001897:Boronic Acids; D003512:Cyclohexanones; D003517:Cyclopentanes; D007659:Ketones; D010720:Phosphines; D012238:Rhodium; C044646:phosphine; C010686:benzeneboronic acid
keywords: arylation; asymmetric catalysis; density functional calculations; diphosphanes; rhodium