title: A mechanistic investigation of the kinetic resolution of secondary aromatic alcohols using a ferrocene-based planar chiral 4-(dimethylamino)pyridine catalyst.
abstract: A detailed computational and kinetic analysis of the acetylation of 1-phenylethanol with acetic anhydride catalyzed by planar chiral 4-(dimethylamino)pyridine (DMAP) catalyst (-)-1 is presented. The study includes a computational investigation of the potential-energy surface including the acylation and stereoselective transition states at the DFT level of theory. Experimentally, the kinetic study shows that the reaction proceeds in a first-order manner in catalyst, whereas both substrates, acetic anhydride and 1-phenylethanol, show fractional order, which is in accordance with steady-state conditions. The fractional order depends on an equilibrium between the free catalyst and the acetylated catalyst.
authors: Department of Chemistry-BMC, Uppsala University, Box 576, 75123, Uppsala (Sweden).
authors: Laura
authors: L
authors: Mesas-Sánchez
authors: Peter
authors: P
authors: Dinér
keywords: acylation; chirality; density functional calculations; kinetics; nucleophilic addition