Studying Regioisomer Formation in the Pd-Catalyzed Fluorination of Cyclic Vinyl Triflates: Evidence for in situ Ligand Modification.

ABSTRACT: Pd-catalyzed nucleophilic fluorination reactions are important methods for the synthesis of fluoroarenes and fluoroalkenes. However, these reactions can generate a mixture of regioisomeric products that are often difficult to separate. While investigating the Pd-catalyzed fluorination of cyclic vinyl triflates, we observed that the addition of a substoichiometric quantity of TESCF₃ significantly improved the regioselectivity of the reaction. Herein, we report a combined experimental and computational study on the mechanism of this transformation focusing on the role of TESCF₃ . The poor regioselectivity of the reaction in the absence of additives results from the formation of LPd-cyclohexyne complexes (L=biaryl monophosphine ligand). When TESCF₃ is added to the reaction mixture, the generation of the Pd-cyclohexyne complexes is diminished by an unexpected pathway involving the dearomatization of the ligand by nucleophilic attack from a trifluoromethyl anion (CF₃ ^- ).

SUBMITTER: Ye Y 

PROVIDER: S-EPMC10161128 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature