Palladium-catalyzed C-C coupling under thermomorphic conditions

Liquid-liquid biphasic systems that exhibit an increase in phase miscibilit y at elevated temperature together with soluble polymer-bound catalysts tha t have a strong phase preference at ambient temperature are described. In s uch systems, product isolation and catalyst recovery are effected by a liqu id/liquid separation. This report-describes the use of such thermomorphic c atalyst recovery systems for palladium-catalyzed carbon-carbon bond forming reactions. Poly(N-isopropylacrylamide) (PNIPAM)-bound phosphine ligands wi th a Pd(0) catalyst used previously in allylic substitution chemistry are e fficient catalysts in Heck, Suzuki, and sp-sp(2) cross-coupling reactions. Air-stable tridentate SCS-Pd(II) catalysts bound to PNIPAM or poly(ethylene glycol) (PEG) are also described. A particular advantage of these SCS cata lysts is that no precautions against adventitious catalyst oxidation need b e taken with the polymer-bound SCS-PdCl catalysts; thus avoiding time-consu ming solvent purification and degassing protocols.