In summary, we have developed a highly efficient protocol to
synthesize o-acylazobenzenes through the Pd(II)-catalyzed C−
H bond activation of azobenzenes with toluene derivatives.
Toluene could be used as an ideal acylation reagent in this
transformation. Meanwhile, diacylazobenzenes were obtained
when TBHP loading was increased. Moreover, the mild
reaction conditions together with operational simplicity would
provide an unprecedented capacity in the installation of various
versatile functional groups at various positions of the
azobenzene. It could be applied to the synthesis of natural
products and other available compounds.