A Mechanistic Investigation of the Kinetic Resolution of Secondary Aromatic Alcohols Using a Ferrocene-Based Planar Chiral 4-(Dimethylamino)pyridine Catalyst

作者：Mesas Sanchez Laura; Diner Peter^*

来源：Chemistry - A European Journal, 2015, 21(14): 5623-5631.

DOI：10.1002/chem.201405793

• acylation
• chirality
• density functional calculations
• kinetics
• nucleophilic addition

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.

• 出版日期2015-3-27