A highly efficient and practical strategy for regio-selective ortho-halogenation (I, Br, Cl) of azoxybenzenes with NXS in the presence of palladium catalysts has been developed in good to excellent yields. The reaction proceeds smoothly and can tolerate a variety of functional groups. Moreover, this chemistry can be applied to substrates in at least a gram scale.

•An efficient and mild protocol for regioselective synthesis of N-Nitroso aryl ketones is described.•This chemistry offered a convenient access to a range of indazoles.•Palladium-catalyzed decarboxylative ortho-acylation of CH bond is very important.An efficient and mild protocol for regioselective synthesis of N-Nitroso aryl ketones by palladium-catalyzed direct acylation of arenes using N-Nitroso as directing groups is described. This reaction proceeded smoothly and could tolerate a variety of functional groups. Moreover, this chemistry offers a convenient access to a range of indazoles.

A palladium-catalyzed regio-selective acylation of C–H bonds of azoxybenzenes with alcohols was developed using tert-butyl hydroperoxide (TBHP) as an oxidant. Alcohol derivatives can act as effective acyl precursors in situ, which are less toxic, inexpensive, stable, and commercially available. These transformations proceeded smoothly and could tolerate a variety of functional groups.

A palladium-catalyzed regio-selective acylation of C–H bonds of azoxybenzenes with alcohols was developed using tert-butyl hydroperoxide (TBHP) as an oxidant. Alcohol derivatives can act as effective acyl precursors in situ, which are less toxic, inexpensive, stable, and commercially available. These transformations proceeded smoothly and could tolerate a variety of functional groups.

A palladium catalyzed efficient strategy for regio-selective ortho-arylation of sulfoxides with benzoyl peroxides via decarboxylation has been developed. This reaction proceeds smoothly, tolerates a variety of functional groups, and provides easy access to the synthesis of different biaryl compounds.

A highly efficient and practical strategy for regio-selective ortho-halogenation (I, Br, Cl) of azoxybenzenes with NXS in the presence of palladium catalysts has been developed in good to excellent yields. The reaction proceeds smoothly and can tolerate a variety of functional groups. Moreover, this chemistry can be applied to substrates in at least a gram scale.