A one-step catalytic synthesis of 6-substituted 4-phenyl-2-(2'-pyridyl)quinolines provides electronically differentiated ligands without solvent, inert atmosphere, metal contamination, or chromatography. Gold(III) complexes formed from these bidentate PyQuin ligands were characterized and studied by single-crystal X-ray diffraction. The cationic gold(III) chloride synthesized from 6-methoxy-4-phenyl-2-(2'-pyridyl)quinoline has a distorted square-planar ligand environment. Diamagnetic neutral gold(III) complexes from methoxy-, methyl-, and phenyl-PyQuin ligands exhibit a long axial Au-N2 interaction.
A simple procedure for the intermolecular enantioselective palladium-catalyzed decarboxylative allylation of β-ketoacids is described. This method, inspired by a stoichiometric control experiment performed by Saegusa and co-workers some 40+ years ago, makes use of allyl carbonates as the coupling substrates and enables direct access to α-allylated ketones bearing newly formed quaternary stereocenters. Experiments suggest that the transformation proceeds via an inner-sphere mechanism and not the traditional outer-sphere process proposed. The reaction should be highly useful and its application is demonstrated by a short enantioselective synthesis of (+)-adalinine.
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