Allylic arylation of allylic acetates by sodium tetraarylborates in the presence of ppb to ppm (molar) loadings of a palladium NNC-pincer complex catalyst in methanol at 50 °C gave the corresponding arylated products in excellent yields. Total turnover numbers of up to 500,000,000 and turnover frequencies of up to 11,250,000 h(-1) were achieved.
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http://dx.doi.org/10.1039/c4cc09726b | DOI Listing |
Chem Asian J
November 2019
Institute for Molecular Science, SOKENDAI, The Graduate University for Advanced Studies), and JST-ACCEL, Myodaiji, Okazaki, 444-8787, Japan.
A palladium NNC-pincer complex at a 5 mol ppm loading efficiently catalyzed the Hiyama coupling reaction of aryl bromides with aryl(trialkoxy)silanes in propylene glycol to give the corresponding biaryls in excellent yields. This method was applied to the syntheses of adapalene and a biaryl-type liquid-crystalline compound, as well as to the derivatization of dextromethorphan and norfloxacin. ESI-MS and NMR analyses of the reaction mixture suggested the formation of pentacoordinate spirosilicate intermediates in situ.
View Article and Find Full Text PDFDalton Trans
May 2015
Institute for Molecular Science, Okazaki 444-8787, Japan.
Two amphiphilic palladium NNC-pincer complexes bearing hydrophilic tri(ethylene glycol) chains and hydrophobic dodecyl chains were designed and prepared for the development of a new aquacatalytic system. In water, these amphiphilic complexes self-assembled to form vesicles, the structures which were established by means of a range of physical techniques. When the catalytic activities of the vesicles were investigated in the arylation of terminal alkynes in water, they were found to catalyze the reaction of aryl iodides with terminal alkynes to give good yields of the corresponding internal alkynes.
View Article and Find Full Text PDFChem Commun (Camb)
March 2015
Institute for Molecular Science, Okazaki 444-8787, Japan.
Allylic arylation of allylic acetates by sodium tetraarylborates in the presence of ppb to ppm (molar) loadings of a palladium NNC-pincer complex catalyst in methanol at 50 °C gave the corresponding arylated products in excellent yields. Total turnover numbers of up to 500,000,000 and turnover frequencies of up to 11,250,000 h(-1) were achieved.
View Article and Find Full Text PDFInorg Chem
September 2005
Department of Chemistry, Western Washington University, Bellingham, Washington 98225, USA.
The sterically crowded isoindoline pincer ligand, 6'-MeLH, prepared by condensation of 4-methyl-2-aminopyridine and phthalonitrile, exhibits very different reaction chemistry with Cd2+, Zn2+, and Pd2+. Three different ligand coordination modes are reported, each dependent upon choice of metal ion. This isoindoline binds to Cd2+ as a charge-neutral, zwitterionic, bidentate ligand using imine and pyridine nitrogen atoms to form the eight-coordinate fluxional complex, Cd(6'-MeLH)2(NO3)2.
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