Ligand controlled orthogonal base-assisted direct C–H bond arylation in oxa(thia)zole-4-carboxylate series. New insights in nCMD mechanism

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Alkyl- and arylphosphines have been screened in competitive C2–H/C5–H direct phenylation of oxa(thia)zole-4-carboxylates using Cs2CO3 and Rb2CO3 carbonate bases. nCMD-based C2–H selective direct phenylation was highly kinetically reduced (or enhanced) in favor (or to the detriment) of CMD-based direct C5–H phenylation with bromo- and chlorobenzene, respectively, using highly electron-rich ligands. These results gave novel experimental proof in favor of the electrophilic substitution-type mechanism for nCMD process based upon a prior nitrogen-arylpalladium complex interaction that preludes the deprotonation step.