Solvent and base dependence of copper-free palladium-catalyzed cross-couplings between terminal alkynes and arylic iodides: Development of efficient conditions for the construction of gold(III)/free-base porphyrin dimers

Journal article, 2006

In this paper, our attempts to optimize the Heck alkynylation (copper-free Sonogashira) reaction are presented. An efficient copper-free coupling protocol was needed for the synthesis of gold/zinc porphyrin dimers because previous methods had failed. Previous studies have usually focused on ligands, whereas this work focuses on the choice of solvent and base. The catalytic system throughout the investigation was formed from the stable precursor [Pd-2(dba)(3)center dot CHCl3] together with the ligand triphenylarsine, an easy-to-handle, air-stable ligand. A model study was conducted to examine the dependence of the Heck alkynylation on the solvent and base. The most successful modification proved to be the addition of methanol, as a cosolvent, in combination with a nucleophilic tertiary base. The success of the methanol additive is hypothesized to be caused by the presence of a rate-determining deprotonation step featuring a charge-separated transition state. Finally, the very high yielding and successful synthesis of a series of porphyrin systems using these new conditions is presented. For the first time, gold porphyrin substrates could efficiently be coupled in Heck alkynylation reactions.