Highly convenient amine-free sonogashira coupling in air in a polar mixed aqueous medium by trans- and cis-[(NHC)2PdX2] (X=Cl, Br) complexes of N/O-functionalized N-heterocyclic carbenes.
Two new trans- and cis-[(NHC)(2)PdX(2)] (X=Cl, Br) complexes of N/O-functionalized N-heterocyclic carbenes employed in a highly convenient amine-free Sonogashira cross-coupling reaction in air in a polar mixed aqueous medium are reported. Specifically, the trans-[{1-benzyl-3-(3,3-dimethyl-2-oxobutyl)imidazol-2-ylidene}(2)PdBr(2)] (3) and cis-[{1-benzyl-3-(N-tert-butylacetamido)imidazol-2-ylidene}(2)PdCl(2)] (4) complexes effectively catalyzed the Sonogashira cross-coupling reaction of aryl iodides with substituted acetylenes in air in a mixed solvent (DMF/H(2)O, 3:1 v/v) under amine-free conditions. Interestingly, these trans- and cis-[(NHC)(2)PdX(2)] (X=Cl, Br) complexes, with two N-heterocyclic carbene ligands, exhibited superior activity compared with the now popular PEPPSI (pyridine enhanced precatalyst preparation, stabilization and initiation)-themed analogues, trans-[(NHC)Pd(pyridine)X(2)] (X=Cl, Br), 3 a and 4 a, with one N-heterocyclic carbene ligand and a "throw away" pyridine ligand in a trans disposition to each other. The higher activities of 3 and 4 compared with PEPPSI analogues 3 a and 4 a are attributed to more-electron-rich metal centers, as revealed by DFT studies, in the former complexes and is in concurrence with a more electron-rich metal center being effective in facilitating the oxidative addition of aryl halide, often a rate-determining step in palladium-mediated cross-coupling reactions. Complexes 3 and 4 were prepared from the corresponding silver analogues by transmetalation with [(cod)PdCl(2)], whereas the corresponding PEPPSI analogues 3 a and 4 a were obtained directly from the imidazolium halide salts by reaction with PdCl(2) in pyridine in the presence of K(2)CO(3) as base.
Ray
Lipika
L
Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai, India.
Barman
Samir
S
Shaikh
Mobin M
MM
Ghosh
Prasenjit
P
D006571:Heterocyclic Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D021241:Spectrometry, Mass, Electrospray Ionization; D013055:Spectrophotometry, Infrared; D014867:Water / Q000737:chemistry*
D006571:Heterocyclic Compounds; D014867:Water; C030011:carbene; D008697:Methane