RESUMO
In investigating potential control factors that would permit a palladium-catalyzed benzylic vs arene C-H activation as previously reported by our group, it was discovered that the oxidation state of the homogenous palladium species influences the selectivity of C-H activation. DFT calculations show that Pd0 and PdI preferentially activate the sp3 C-H bond in toluene, whereas PdII and PdIII preferentially activate the sp2 C-H bond. This selectivity appears to originate from the steric environment created by the ligand framework on the palladium. As the palladium oxidation state increases, the number of ligand sites increases, which decreases the energetic favorability for activation of the weaker, yet more hindered sp3 C-H bond.
RESUMO
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.
