TY - JOUR
T1 - Computational rationalization of the dependence of the enantioselectivity on the nature of the catalyst in the vanadium-catalyzed oxidation of sulfides by hydrogen peroxide
AU - Balcells, David
AU - Maseras, Feliu
AU - Ujaque, Gregori
PY - 2005/3/16
Y1 - 2005/3/16
N2 - A computational study with the IMOMM(Becke3LYP:MM3) method is carried out on the mechanism of the enantioselective reaction of complex V(O)(L)(OOH), L= bulky tridentate Schiff base, and bis(tert-butyl) disulfide. The reaction with a given L ligand A is first systematically studied: different conformers of the catalyst are optimized, and the large number of associated transition states are systematically searched. The study is then extended to the geometry optimization of selected transition states associated to other ligands B, C, and D, similar to A but differing in the nature of certain substituents R 1, R2, R3. The experimental trends in selectivity for catalysts based on ligands A to D are faithfully reproduced by the calculations. Analysis of the computational results leads finally to the formulation of a simple model that can explain one of the most remarkable aspect of this reaction, namely the large effect on enantioselectivity of ligands seemingly far from each other in the catalyst. © 2005 American Chemical Society.
AB - A computational study with the IMOMM(Becke3LYP:MM3) method is carried out on the mechanism of the enantioselective reaction of complex V(O)(L)(OOH), L= bulky tridentate Schiff base, and bis(tert-butyl) disulfide. The reaction with a given L ligand A is first systematically studied: different conformers of the catalyst are optimized, and the large number of associated transition states are systematically searched. The study is then extended to the geometry optimization of selected transition states associated to other ligands B, C, and D, similar to A but differing in the nature of certain substituents R 1, R2, R3. The experimental trends in selectivity for catalysts based on ligands A to D are faithfully reproduced by the calculations. Analysis of the computational results leads finally to the formulation of a simple model that can explain one of the most remarkable aspect of this reaction, namely the large effect on enantioselectivity of ligands seemingly far from each other in the catalyst. © 2005 American Chemical Society.
U2 - 10.1021/ja0435384
DO - 10.1021/ja0435384
M3 - Article
VL - 127
SP - 3624
EP - 3634
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 10
ER -