We disclose a pair of ortho-sulfinylaniline auxiliaries for palladium-catalyzed β–C-H arylation of alkyl carboxamides. Together, these auxiliaries offer a means to effect efficient β-methyl and methylene C–H bond arylation with sterically hindered aryl iodides. ortho-Methylsulfinylaniline (MSOA) enables efficient β-methyl C–H arylation of propanamide substrates with aryl iodides bearing various ortho-substituents including alkyl groups. ortho-Tosylsulfinylaniline (TSOA) enables β-methylene C–H arylation with ortho-substituted aryl iodides. Both amide-linked MSOA and TSOA auxiliaries can be easily removed to give ester products under relatively mild conditions.Keywords: hindered aryl iodide; methylene C−H; palladium; sp3 C−H arylation; sulfinylaniline auxiliary;

An iridium-catalyzed ortho-C(sp2)–H amidation reaction of benzaldehydes with organic azides has been developed. A catalytic amount of 3,5-di(trifluoromethyl)aniline was used to promote the Ir-catalyzed directed C–H amination reaction through a transient aldimine intermediate. This reaction tolerates a broad scope of benzaldehyde substrates and works well with a range of aryl- and alkylsulfonyl azides.