An unprecedented copper acetate-DMSO promoted methylthiolation of arenes and heteroarenes in the presence of air has been developed. The reaction is highly regioselective under the directing group influence of pyridine and pyrimidine functional units and gives the thiomethylated product in moderate to high yields.

We describe a modular, palladium catalyzed synthesis of aryl(hetero)aryl benzophenones and aryl benzoates from aryl(hetero)aryl halides using CHCl as the carbonyl source in the presence of KOH. The reaction occurs in tandem through an initial carbonylation to generate an aroyl halide, which undergoes coupling with arylboronic acids, bornonates, and phenols. Direct carbonylative coupling of indoles at the third position has also been accomplished under slightly modified reaction conditions by in situ activation of the C-H bond. Notably, CHCl is a convenient and safe alternation of CO gas, provides milder reaction conditions with high functional group tolerance, and gives the products in moderate to good yields.

d-Mannose as a ligand for Pd catalyzed cross-coupling, and as a hydrogen source for nitro reduction in a modular one-pot cross coupling-nitro reduction sequence.

A copper acetate catalyzed oxidative cycloaddition reaction of benzyl and aryl azides with terminal and internal olefins that contain electron-withdrawing groups (COOR, CONH 2 , CN, CHO, COR) has been developed. The reaction em-

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