- Author
- Year
- 2008
- Title
- Insights into Sonogashira cross-coupling by high-throughput kinetics and descriptor modeling
- Journal
- Chemistry - A European Journal
- Volume | Issue number
- 14 | 9
- Pages (from-to)
- 2857-2866
- Document type
- Article
- Faculty
- Faculty of Science (FNWI)
- Institute
- Swammerdam Institute for Life Sciences (SILS)
- Abstract
-
A method is presented for the high-throughput monitoring of reaction kinetics in homogeneous catalysis, running up to 25 coupling reactions in a single reaction vessel. This method is demonstrated and validated on the Sonogashira reaction, analyzing the kinetics for almost 500 coupling reactions. First, one-pot reactions of phenylacetylene with a set of 20 different meta- and para-substituted aryl bromides were analyzed in the presence of 17 different Pd-phosphine complexes. In addition, the temperature-dependent Sonogashira reactions were examined for 21 different ArX (X = Cl, Br, I) substrates, and the corresponding activation enthalpies and entropies were determined by means of Eyring plots: ArI (ΔH≠ = 48-62 kJ mol-1; ΔS≠ = -71-39 J mol-1 K; NO2→OMe), ArBr (ΔH≠ = 54-82 kJ mol-1, ΔS ≠ = -55-11 J mol-1 K), and ArCl (ΔH ≠ = 95-144 kJ mol-1, ΔS≠ = -6-100 J mol-1 K). DFT calculations established a linear correlation of ΔH≠ and the Kohn-Sham HOMO energies of ArX (X = Cl, Br, I) and confirmed their involvement in the rate-limiting step. However, despite different C-X bond energies, aryl iodides and electron-deficient aryl bromides showed similar activation parameters.
- URL
- go to publisher's site
- Other links
- Link to publication in Scopus
- Language
- English
- Persistent Identifier
- https://hdl.handle.net/11245/1.293473
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