Copper(ii)-catalyzed Chan-Lam cross-coupling: chemoselective N-arylation of aminophenols.

Copper(ii)-catalyzed boronic acid promoted chemoselective N-arylation of unprotected aminophenols has been developed. Selective N-arylation of 3-aminophenol is achieved with a Cu(OAc)2/AgOAc combination in MeOH at rt, whereas the chemoselective N-arylated products of 4-aminophenol can be obtained with a Cu(OAc)2/Cs2CO3 system and benzoic acid as an additive. These ligand-free conditions and "open-flask" chemistry are robust and compatible with a wide range of functional groups. The mechanistic investigation for this selective N-arylation has been studied by considering Density Functional Theory (DFT) calculations.

Palladium/Silver Synergistic Catalysis in Direct Aerobic Carbonylation of C(sp(2))-H Bonds Using DMF as a Carbon Source: Synthesis of Pyrido-Fused Quinazolinones and Phenanthridinones.

An unprecedented Pd/Ag synergistic catalysis in the direct carbonylation of C(sp(2))-H bonds utilizing DMF as the carbon source under oxygen is described and demonstrated in the synthesis of pyrido-fused quinazolinone and phenanthridinone scaffolds. Control experiments indicated that the "C" of the carbonyl group is derived from the methyl group of DMF and "O" originates from oxygen as in the case of Ge's recent work. This transformation offers an alternative avenue for "CO-free" carbonylations.