No compass required: A method is described for forming biaryl CC bonds by a PdII‐catalyzed cross‐coupling of aryl CH bonds with aryl boronic acids under mild conditions without the presence of directing groups. Different substituents on both (hetero)arenes and aryl boronic acids are compatible with the reaction conditions, and the homocoupling of boronic acids is highly inhibited. Dioxygen was applied as the final oxidant.

Highly regioselective olefination of substituted N,N-dimethylbenzylamines was developed by tuning the acidity of reaction conditions based on analysis of their features. The ortho-functionalized N,N-dimethylbenzylamines were further transformed into 3-(2'-tolyl)propanoic acid and its derivatives under mild conditions. These two transformations could be combined into one pot, and 3-(2'-tolyl)propanoic acid and its derivatives were obtained in moderate to good yields. Mechanistic studies indicated that electrophilic attack on the phenyl ring by the Pd(II) ion assisted by the N,N-dimethylaminomethyl group was a key step during this catalytic transformation, which was controlled by the acidity of the reaction conditions.