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

• Published in: Journal of organic chemistry Vol. 71; no. 4; pp. 1677 - 1687
• Main Authors: Ljungdahl, Thomas, Pettersson, Karin, Albinsson, Bo, Mårtensson, Jerker
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 17.02.2006; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; VINYL; MECHANISM; AMINES; ACETYLENE; PALLADACYCLES; COMPLEXES; REACTIVITY; BROMIDES; LIGAND TRANSFER; STILLE REACTION; Alkynylation; Transition element complexes; Acetylenic compound; Ligand; Heck reaction; Palladium complex; Organic iodine compounds; Cross reaction; Chemical synthesis; Solvent; Deprotonation; Methanol; Gold; Catalytic reaction; Transition metal; Air; Reaction rate; Zinc; Cosolvent; Copper ion; Porphyrin; Transition state; Platinoid Complexes; Dimer; Alkyne; Nucleophile
• ISSN: 0022-3263; 1520-6904; 1520-6904
• DOI: 10.1021/jo052423v

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 [Pd2(dba)3·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.