Transition-metal-catalyzed carbon-hydrogen (C–H) bond activation
reaction is one of the most straightforward methods in organic transformations
[1–7]. Among them, Pd catalysis is widely utilized [8–14]. In
these cases, carboxylic acids, typically pivalic acid, play an important
role as the ligand in C–H bond activation step via concerted metalation
deprotonation (CMD) mechanism [15–17]. Fagnou reported that the
Pd-catalyzed intramolecular C(sp3
)–H bond arylation reactions
proceeded efficiently with pivalic acid as the ligand (Scheme 1a) [18].
In the reaction, acetic acid was not so effective. Fagnou also reported
that pivalic acid was more effective ligand than acetic acid in the Pd-catalyzed
intermolecular C(sp2
)–H arylation with aryl bromides (Scheme
1b) [19]. Therefore, it is interesting to see how steric effect of the carboxylic
acids (carboxylates) influences the C–H bond activation reactions.
Recently, Thompson investigated the effect of various carboxylic
acids on the Pd-catalyzed direct arylation polymerization with 3-
hexylthiophene [20]. However, it is still unclear how the nature of carboxylic
acid ligands affects the C–H bond activation reactions.