Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF3∙OEt2-catalyzed C‒F bond activation

Ag2CO3-Promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source. The reaction involves β-fragmentation of primary alkoxy radicals, followed by the fluorination of the resulting C-centered radical intermediates. The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope, thus opening up a new entrance to the synthesis of fluorinated constructs including α-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives. The divergent functionalization of the obtained α-fluoroimides enables an efficient access to amine derivatives through C–F bond activation under the action of BF3∙OEt2.