A general protocol for the palladium-catalyzed carbonylation of aryl tosylates and mesylates to form esters has been developed using a catalyst system derived from Pd(OAc)2 and the bulky, bidentate dcpp ligand. The system operates under mild conditions: atmospheric CO pressure and temperatures of 80-110 degrees C. A broad substrate scope has been demonstrated allowing carbonylation of electron-rich, electron-poor, and heterocyclic tosylates and mesylates, and the reaction shows wide functional group tolerance.
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http://dx.doi.org/10.1021/ja711449e | DOI Listing |
Nucl Med Biol
December 2024
Department of Radiology, University of Pennsylvania; Philadelphia, PA, USA. Electronic address:
Direct fluorination of a tosylate or mesylate precursor has been a wide-spread and reliable way for radio-fluorination. This approach can be difficult to achieve when the precursor cannot be easily obtained or is chemically unstable. A possible alternative method is to radiolabel ethylene ditosylate or 1,3-propanediol di-p-tosylate to form a radiofluorinated synthon.
View Article and Find Full Text PDFACS Omega
July 2024
Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, 1111 Budapest, Hungary.
α-Hydroxyphosphonates and their acylated and phosphorylated derivatives may be of significant biological activity including cytotoxic effects. To extend the pool of the potentially bioactive species, new methane- and arenesulfonyloxyphosphonates were synthesized by the sulfonylation of differently substituted α-hydroxy-benzylphosphonates using methanesulfonyl chloride or -toluenesulfonyl chloride at 25 °C in the presence of triethylamine in toluene. The new sulfonyl derivatives were obtained in 54-80% yields.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2024
Department of Chemistry, University of California, Irvine, California, 92617, United States.
Nickel-catalyzed cross-electrophile coupling reactions of two aliphatic alcohol derivatives remain a challenge. Herein, we report a nickel-catalyzed reductive methylation reaction of aliphatic mesylates with methyl tosylate. This reaction provides straightforward access to compounds bearing aliphatic methyl groups from alkyl alcohol derivatives.
View Article and Find Full Text PDFInt J Pharm
March 2024
Área de Análisis de Medicamentos, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario e Instituto de Química Rosario (IQUIR. CONICET-UNR), Suipacha 531, S2002LRK, Rosario, Argentina. Electronic address:
Acta Crystallogr E Crystallogr Commun
September 2023
Department of Chemistry-Box H, Brown University, Providence, Rhode Island 02912, USA.
The structures of three racemic (tetra-hydro-[1,3]dioxino[5,4-][1,3]dioxin-4-yl)methanol derivatives are reported, namely, 4-[(methyl-sulfon-yloxy)meth-yl]-2,4,4a,6,8,8a-hexa-hydro-[1,3]dioxino[5,4-][1,3]dioxine, CHOS, , 4-[(benz-yloxy)meth-yl]-2,4,4a,6,8,8a-hexa-hydro-[1,3]dioxino[5,4-][1,3]dioxine, CHO, , and 4-[(anilinocarbon-yl)meth-yl]-2,4,4a,6,8,8a-hexa-hydro-[1,3]dioxino[5,4-][1,3]dioxine, CHNO, . Mesylate ester at 173 K has triclinic symmetry and both benzyl ether at 173 K and phenyl urethane have monoclinic 2/ symmetry. These structures are of inter-est because of the conformation of the -fused tetra-oxadeca-lin ring system.
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