Mild and room temperature C-C bond forming reactions of nucleoside C-6 arylsulfonates.
[reaction: see text] Palladium catalyzed cross coupling of nucleoside arylsulfonates and arylboronic acids has been accomplished under mild conditions and at room temperature. Among three structurally similar ligands that differ in their steric and electronic properties, one yielded an effective catalyst in conjunction with Pd(OAc)2. Of the nucleoside arylsulfonates evaluated, the O6-(2,4,6-trimethylphenyl)sulfonate proved optimal, but other alkyl and alkoxy derivatives were also reasonably reactive. On the other hand, a 2-nitrophenyl and a 2-thienyl derivative were ineffective substrates. PhMe and THP were suitable as solvents, yielding good results in several cases, although reactions of some arylboronic acids were faster in PhMe. In contrast, reactions of arylboronic acids bearing strongly electron-withdrawing groups proceeded more successfully in THP. Interplay between several factors that include substituents on the nucleoside arylsulfonate, ligand substituents, and solvent is responsible for successful cross coupling. Using 31P NMR, an initial investigation has been conducted to study the interaction of Pd(OAc)2 with the ligand. At a 1:1 stoichiometry of ligand and Pd(OAc)2, a predominant species, likely a cyclopalladation product, was obtained. At a 2:1 ratio of ligand and Pd(OAc)2, a different species bearing chemically distinct phosphine ligands was observed. Both complexes display catalytic activity, although the 2:1 species may be superior.
Lakshman
Mahesh K
MK
Department of Chemistry, The City College and The City University of New York, 138th Street at Convent Avenue, New York, New York 10031-9198, USA. lakshman@sci.ccny.cuny.edu
Gunda
Padmaja
P
Pradhan
Padmanava
P
D001190:Arylsulfonates / Q000138:chemical synthesis*; D002384:Catalysis; D009705:Nucleosides / Q000138:chemical synthesis*; D010165:Palladium; D012997:Solvents; D013696:Temperature
D001190:Arylsulfonates; D009705:Nucleosides; D012997:Solvents; D010165:Palladium