tBu or not tBu?

Chemistry

Department of Chemistry and Molecular Biology, University of Gothenburg, Kemigården 4, 412 96 Göteborg, Sweden.

Published: February 2012

The regioselectivity in the palladium-catalyzed Heck coupling reaction between an aryl halide and ethyl vinyl ether with four different phosphine ligands: PPh(n)tBu(m) (n=0-3, m=3-n) has been investigated both experimentally and computationally. A zigzag selectivity pattern was experimentally observed upon consecutive replacement of Ph by tBu in the phosphine ligand. Use of a standard DFT method (B3LYP) was shown to give a correct prediction of product preference. However, the trend in relative selectivity among the different ligands could not be correctly described. The use of a more recent DFT functional (M06) parameterized to reproduce dispersion interactions resulted in an improved description. For the sterically most demanding ligands, PtBu(3) and PPhtBu(2), unexpectedly large deviations between experimental and M06 calculated selectivities raised the question of an alternative mechanism for these ligands. In the case of PtBu(3) it was found, in agreement with literature data, that the phosphine ligand could be replaced by a second halide ligand, resulting in an anionic mechanism, with a calculated selectivity in excellent agreement with experimental data. For the PPhtBu(2) ligand, two mechanisms are suggested to operate in parallel, as demonstrated both by computational studies and experimental observation of halide-dependent selectivity. A Halpern effect is observed for all phosphine ligands investigated, that is, the least stable pre-complex results in the most abundant product.

Download full-text PDF

Source
http://dx.doi.org/10.1002/chem.201102674DOI Listing

Publication Analysis

Top Keywords

phosphine ligands
8
phosphine ligand
8
ligands
5
tbu tbu?
4
tbu? regioselectivity
4
regioselectivity palladium-catalyzed
4
palladium-catalyzed heck
4
heck coupling
4
coupling reaction
4
reaction aryl
4

Similar Publications

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!