A novel palladium-catalyzed intermolecular aminofluorination of styrenes, with N-fluorobenzenesulfonimide (NFSI) functioning not only as a fluorinating reagent but also as an aminating reagent, has been developed. The reaction afforded vicinal fluoroamine products with very high regioselectivity. This transformation may involve fluoropalladation of styrene as a key step for C-F bond formation. The bidental nitrogen ligand is crucial to achieving the transformation successfully.
A novel palladium-catalyzed intramolecular aerobic oxidative allylic C-H amination of olefins has been developed. Brønsted base can modulate the regioselectivity, favoring the formation of 7-membered rings. Mechanistic studies using deuterium-labeled substrates as probes support a rate-determining allylic C-H activation/irreversible reductive elimination pathway.
Taking the air! A Pd(II)-catalyzed intramolecular hydroamination of allenes coupled to alcohol oxidation has been developed. This reaction is performed by using a nitrogen-based ligand under aerobic conditions, under which the molecular oxygen is used as the terminal oxidant for the reoxidation of Pd(0) species to complete the catalytic cycle.
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