Kinetic studies on sec-alcohol racemization with dicarbonylchloro(pentabenzylcyclopentadienyl)- and dicarbonylchloro(pentaphenylcyclopentadienyl)ruthenium catalysts

A1 Journal article (refereed)


Internal Authors/Editors


Publication Details

List of Authors: Denys Mavrynsky, Dmitry Yu. Murzin, Reko Leino
Publisher: WILEY-V C H VERLAG GMBH
Publication year: 2013
Journal: ChemCatChem
Journal acronym: CHEMCATCHEM
Volume number: 5
Issue number: 8
Start page: 2436
End page: 2445
Number of pages: 10
ISSN: 1867-3880
eISSN: 1867-3899


Abstract

Pentasubstituted cyclopentadienyl complexes of ruthenium R5CpRu(CO)(2)Cl (R=Ph, benzyl) form, upon activation with tBuOK, highly active catalysts for racemization of chiral sec-alcohols. In combination with suitable resolving enzymes, such catalyst systems can efficiently be utilized for dynamic kinetic resolution reactions providing chiral alcohols, after hydrolysis of the corresponding acetates, in high yields and high enantiomeric purities. Here, three such ruthenium complexes were first characterized by NMR spectroscopy and cyclic voltammetry analysis (CVA) for elucidating their electronic characteristics in detail. 5CpRu(CO)(2)Cl (Bn=benzyl) racemizes electron-rich substrates more efficiently and in most cases faster than its pentaphenyl substituted analogue, formerly often considered as the leading catalyst candidate for dynamic kinetic resolution applications. 5CpRu(CO)(2)Cl, in turn, is more efficient for electron-poor substrates.


Keywords

alcohols, cyclopentadienyl ligands, kinetics, racemization, ruthenium

Last updated on 2019-15-12 at 04:44

Share link