A Pd(II)-catalyzed arylation of methylene C(sp(3))-H bonds in aliphatic amides directed by our newly developed PIP directing group with aryl iodides/bromides has been achieved. Arylation occurs efficiently with a broad range of aryl halides and amides.

A palladium-catalyzed arylation of unactivated γ-methylene C(sp(3) )H and remote δ-CH bonds by using an oxazoline-carboxylate directing group has been developed. Arylation occurs with a broad substrate scope and high tolerance of functional groups (i.e., halogen, nitro, cyano, ether, trifluoromethyl, amine, and ester). The oxazoline-type auxiliary can be removed under acidic conditions.

Stereoselective synthesis of α-amino-β-lactams via Pd-catalyzed sequential C(sp3)–H monoarylation/amidation is described.

The Ru-catalyzed meta-C-H benzylation of arenes bearing pyridyl, pyrimidyl, and pyrazolyl directing groups with toluene derivatives has been reported. Heptafluoroisopropyl iodide (CFI) was employed as both a mild oxidant and radical initiator. This reaction showed excellent site-selectivity and tolerated a wide range of functional groups, providing a new strategy for the synthesis of various diarylmethane moieties.