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

Abstract

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 O 2 are the keys to success.

Silver nitrate promoted synthesis of tetraphenyl derivatives and diaryl ketones

“…9H-Xanthen-9-one (3f). 36 After the reaction according to the general procedure: 9H-xanthene (0.2 mmol), silver nitrate (0.4 mmol), potassium persulfate (0.2 mmol) was added in acetonitrile and water (1: 1) ratio. The resulting mixture was stirred under nitrogen atmosphere at 60 °C for 24 h. The crude mixture was purified by column chromatography (silica gel) using hexane as solvent and obtained as white solid (22 mg, 56%); mp 171-172 °C ; 1 H-NMR (600 MHz, CDCl3) δ 8.36-8.35 (m, 2H), 7.75-7.72 (m, 2H), 7.52-7.50 (m, 2H), 7.41-7.38 (m, 2H); 13 C-NMR (151 MHz, CDCl3) δ177.4, 156.4, 135.0, 126.9, 124.1, 118.1, 116.7.…”