Recent advances in the Pd-catalyzed fluorination of (hetero)aryl halides and triflates using catalysts based on biaryl phosphine ligands are presented.  In-depth mechanistic and stoichiometric studies suggest that the desired cross-coupling cycle, specifically C-F reductive elimination from L-Pd(Ar)F intermediates, is operative during catalytic reactions.  However, two side processes occur in addition to the desired catalytic cycle in certain cases: 1) modification of the ligand via a dearomative rearrangement, and 2) regioisomer formation by in-situ deprotonation of L-Pd(Ar)X (X = Br, OTf) intermediates.  A thorough mechanistic understanding of the mechanistic complexities of Pd-catalyzed fluorination reactions enabled the preparation of new catalysts capable of effecting the fluorination of complex (hetero)aryl halides and triflates, including selected 5-membered heteroaryl bromides, for the first time.

Pd-catalyzed fluorination of (hetero)aryl halides and triflates

253rd National Meeting (2017)

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