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Utilising Sodium‐Mediated Ferration for Regioselective Functionalisation of Fluoroarenes via C−H and C−F Bond Activations
Author(s) -
Maddock Lewis C. H.,
Nixon Tracy,
Kennedy Alan R.,
Probert Michael R.,
Clegg William,
Hevia Eva
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201709750
Subject(s) - regioselectivity , chemistry , sodium , amide , triple bond , medicinal chemistry , stereochemistry , combinatorial chemistry , polymer chemistry , double bond , organic chemistry , catalysis
Pairing iron bis(amide) Fe(HMDS) 2 with Na(HMDS) to form new sodium ferrate base [(dioxane) 0.5 ⋅NaFe(HMDS) 3 ] ( 1 ) enables regioselective mono and di‐ferration (via direct Fe−H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore, using excess 1 at 80 °C switches on a remarkable cascade process inducing the collective twofold C−H/threefold C−F bond activations, where each C−H bond is transformed to a C−Fe bond whereas each C−F bond is transformed into a C−N bond.