Nitrosoarene-Catalyzed HFIP-Assisted Transformation of Arylmethyl Halides to Aromatic Carbonyls under Aerobic Conditions

A rare
metal-free nucleophilic nitrosoarene catalysis accompanied
by highly hydrogen-bond-donor (HBD) solvent, 1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP), organocatalytically converts arylmethyl halides to aromatic
carbonyls. This protocol offers an effective means to access a diverse
array of aromatic carbonyls with good chemoselectivity under mild
reaction conditions. The activation of arylmethyl halides by HFIP
to generate stable carbocation and autoxidation of in situ generated
hydroxylamine to nitrosoarene in the presence of atmospheric O2 are the keys to success.