Cis-specific hydrofluorination of alkenylarenes under palladium catalysis through an ionic pathway

Article abstract of DOI:10.1002/anie.201310056

This paper describes the hydrofluorination of alkenes through sequential H^- and F⁺ addition under palladium catalysis. The reaction is cis specific, thus providing access to benzylic fluorides. The mechanism of this reaction involves an ionic pathway and is distinct from known hydrofluorinations involving radical intermediates. The first catalytic enantioselective hydrofluorination is also disclosed. See attached PdF: A series of benzylic fluorides was prepared by hydrofluorination which proceeds through a Pd^II/IV catalytic manifold. The method is mechanistically distinct from previously reported radical hydrofluorination, and is characterized by its clean regioselectivity and unique cis stereospecificity. The first example of enantioselective net HF addition onto 2-vinylnaphthalene is also disclosed.