(2-Fluoroallyl)pyridinium Tetrafluoroborates: Novel Fluorinated Electrophiles for Pd-Catalyzed Allylic Substitution

An efficient two-step approach to 2-fluoroallyl amines was developed that involves the synthesis of (2-fluoroallyl)pyridinium tetrafluoroborates from readily available gem-bromofluorocyclopropanes and the application of the former as novel and stable 2-fluoroallyl electrophiles for Pd-catalyzed allylic substitution<br /

(2-Fluoroallyl)palladium Complexes as Intermediates in Pd-Catalyzed Tsuji-Trost 2-Fluoroallylations: Synthesis and Reactivity

The first examples of (2-fluoroallyl)palladium complexes were synthesized, isolated and characterized including chloride dimers, neutral chloride and ionic triflate complexes bearing PPh3 or SPhos as the ligands. Preliminary reactivity patterns indicating strong dependence of the chemoselectivity on "hardness" of the nucleophile and the ligand type were studied.<br /