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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

Thomas Ljungdahl (Institutionen för kemi- och bioteknik, Organisk kemi) ; Karin Pettersson (Institutionen för kemi- och bioteknik, Fysikalisk kemi) ; Bo Albinsson (Institutionen för kemi- och bioteknik, Fysikalisk kemi) ; Jerker Mårtensson (Institutionen för kemi- och bioteknik, Organisk kemi)
Journal of Organic Chemistry (0022-3263). Vol. 71 (2006), 4, p. 1677-1687.
[Artikel, refereegranskad vetenskaplig]

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.



Denna post skapades 2007-02-05. Senast ändrad 2017-10-03.
CPL Pubid: 26237

 

Institutioner (Chalmers)

Institutionen för kemi- och bioteknik, Organisk kemi (2006-2014)
Institutionen för kemi- och bioteknik, Fysikalisk kemi (2005-2014)

Ämnesområden

Kemi

Chalmers infrastruktur