Jump to main content
Jump to site search

Issue 45, 2015
Previous Article Next Article

Highly electron-poor Buchwald-type ligand: application for Pd-catalysed direct arylation of thiophene derivatives and theoretical consideration of the secondary Pd0–arene interaction

Author affiliations

Abstract

Highly electron-poor SPhos ligands bearing either 2,6-bis(trifluoromethyl)-4-pyridyl (BFPy) or 3,5-(CF3)2C6H3 groups were synthesised. The former ligand highly accelerated the Pd-catalysed direct arylation of 2-propylthiophene, 2-methylthiophene or benzo[b]thiophene with only 1 mol% of the catalyst. This high catalytic activity can be attributed to a combination of electronic properties and the secondary Pd–arene interaction of BFPySPhos. The secondary interactions of SPhos, PhSPhos and BFPySPhos were optimised at the oniom(mp2/lanl2dz : b3lyp/lanl2dz) level and were further evaluated using the NBO method by DFT at the M06-2X/6-31G(d) level with LanL2DZ + ECP. The deletion energy analysis showed that the transfer of electrons from Pd to aromatic ring is the dominating factor for the secondary Pd–arene interaction of SPhos–Pd0 complexes. Although an electron-poor BFPySPhos does not particularly favour this type of interaction, this interaction is still substantial enough to sufficiently stabilise the BFPySPhos–Pd complex.

Graphical abstract: Highly electron-poor Buchwald-type ligand: application for Pd-catalysed direct arylation of thiophene derivatives and theoretical consideration of the secondary Pd0–arene interaction

  • This article is part of the themed collection: Fluorine
Back to tab navigation

Supplementary files

Publication details

The article was received on 27 May 2015, accepted on 31 Jul 2015 and first published on 31 Jul 2015


Article type: Paper
DOI: 10.1039/C5DT01991E
Author version
available:
Download author version (PDF)
Citation: Dalton Trans., 2015,44, 19642-19650
  •   Request permissions

    Highly electron-poor Buchwald-type ligand: application for Pd-catalysed direct arylation of thiophene derivatives and theoretical consideration of the secondary Pd0–arene interaction

    T. Korenaga, R. Sasaki and K. Shimada, Dalton Trans., 2015, 44, 19642
    DOI: 10.1039/C5DT01991E

Search articles by author

Spotlight

Advertisements