Efficient routes toward activation of gem-chlorofluorocyclopropane-derived (2-fluoroallyl)boronates for allylboration of various ketones including functionalized and low-reactive ones were developed. Increasing the boron electrophilicity by the transformation of a boronate moiety into a borinic ester with n BuLi/trifluoroacetic anhydride (TFAA) makes (2-fluoroallyl)boration of acetyl arenes/hetarenes and aliphatic ketones possible with high diastereoselectivity. For low-reactive or sterically hindered ketones (e.g., benzophenone, adamantanone), "CuF"based catalysts were developed: (NHC)CuF•HF and (NHC)-CuOTf in the presence of an excess of KHF 2 (NHC = IPr, SIPr, IPr Cl ).

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...

The first examples of -(2-fluoroallyl)palladium complexes were synthesised, isolated and characterized including chloride dimers, neutral chloride or cationic triflate comlexes 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.