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Journal of the American Chemical Society, Vol.136, No.14, 5520-5524, 2014
Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic alpha,alpha-Dihaloketones
The development of new approaches to the construction of fluorine-containing target molecules is important for a variety of scientific disciplines, including medicinal chemistry. In this Article, we describe a method for the catalytic enantioselective synthesis of tertiary alkyl fluorides through Negishi reactions of racemic alpha-halo-alpha-fluoroketones, which represents the first catalytic asymmetric cross-coupling that employs geminal dihalides as electrophiles. Thus, selective reaction of a C-Br (or C-Cl) bond in the presence of a C-F bond can be achieved with the aid of a nickel/bis(oxazoline) catalyst. The products of the stereoconvergent cross-couplings, enantioenriched tertiary alpha-fluoroketones, can be converted into an array of interesting organofluorine compounds.