A Mechanistic Investigation of the Kinetic Resolution of Secondary Aromatic Alcohols Using a Ferrocene-Based Planar Chiral 4-(Dimethylamino)pyridine Catalyst
2015 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 21, no 14, 5623-5631 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2015. Vol. 21, no 14, 5623-5631 p.
acylation, chirality, density functional calculations, kinetics, nucleophilic addition
IdentifiersURN: urn:nbn:se:kth:diva-166343DOI: 10.1002/chem.201405793ISI: 000352504500041PubMedID: 25677932ScopusID: 2-s2.0-84925127164OAI: oai:DiVA.org:kth-166343DiVA: diva2:810666
FunderSwedish Research CouncilKnut and Alice Wallenberg Foundation
QC 20150508 QC 201601132015-05-082015-05-072016-01-13Bibliographically approved