An efficient palladium-catalyzed regioselective C-P bond formation of azo compounds through C-H bond functionalization using dialkyl phosphites as phosphorus source under mild conditions was developed. A series of both symmetrical and unsymmetrical azoarenes were successfully phosphonylated through this procedure with tolerance of a broad range of functional groups.

The oxidative activation of alkyl C-H bonds vs arene C-H bonds with Pd(OAc) 2 has been found to be generalizable to a number of nucleophilic substrates allowing the formation of a range of hindered quaternary centers. The substrates share a common mechanistic path wherein Pd(II) initiates an oxidative dimerization. The resultant dimer modifies the palladium catalyst to favor activation of alkyl C-H bonds in contrast to the trends typically observed via a concerted metalation deprotonation mechanism. Notably, insertion occurs at the terminus of the alkyl arene for hindered substrates. Two different oxidant systems were discovered that turn over the process. Parameters have been identified that predict, which substrates are productive in this reaction.

Lewis‐acid‐catalyzed benzylic reactions of 2‐methylazaarenes with aldehydes have been investigated. Series of azaarene derivatives were afforded by this reaction. 2‐(Pyridin‐2‐yl)ethanols with common substituents were formed through the LiNTf2‐promoted aldol reaction for the first time. 2‐Alkenylpyridines, exclusively in the form of the E isomers, were synthesized in the presence of LiNTf2 cooperated with H2NTf. In the presence of La(Pfb)3 as catalysis, 2‐alkenylquinolines were obtained in high yields through the reactions between 2‐methylquinolines and aldehydes under air.

Addition of diarylphosphine oxides to the N═N double bond of azobenzenes leads to the formation of the P-substituted hydrazines in up to 98% yield for 24 examples, and the formation of diphenylphosphinic amides was observed in three substrates. This strategy features tolerance of a wide range of functional groups, simple operation, and mild reaction conditions. Specially, this method can be also applied to the gram-scale synthesis of the product. A polar reaction mechanism is also proposed based on control experiments.