Electrolytic partial fluorination of organic compounds. 77. Reactivity of anodically generated benzylic cation intermediates toward fluoride ions in acetonitrile

Visible Light-Promoted Metal-Free C–H Activation: Diarylketone-Catalyzed Selective Benzylic Mono- and Difluorination

“…Currently, there is no report of selective gem -difluorination using C–H activation methods. Traditional electron-transfer methods gave little control on the degree of fluorination . Therefore, gem -difluorides are usually synthesized by deoxodifluorination of ketones or dethiodifluorination of dithianes .…”

Electrolytic partial fluorination of organic compounds 84

“…This trend cannot be explained by substituent effects of a methoxy group. Initial electron-transfer seems to take place at the methoxy group instead of benzene ring, similarly to the case of p-methoxy isopropylbenzene [8]. Moreover, a p-iodo substituent also decreased the oxidation potentials appreciably.…”

“…a-Monofluorinated and a,a-difluorinated products were obtained respectively depending on electricity passed as shown in Scheme 1. We also studied systematically anodic benylic fluorination of various aromatic compounds [8]. Moreover, quite recently we have successfully prepared cyclic amonofluorophosphonate esters by using anodic fluorination and ring-closing olefin methathesis as shown in Scheme 2 [9].…”

Direct Acetoxylation of Arenes

“… a Data taken from refs − . Arene (1.0 mmol) in AcOH (0.5 mL) was added to a suspension of NaNO 3 (2.2 mmol), TFA (0.5 mL), Ac 2 O (1.1 mmol) and AcOH (1.0 mL) at rt and the reaction mixture was stirred at rt for 14 h. b In V vs SCE. c The reaction was conducted at 0 °C. d A 1:1 mixture of 3-methoxynaphthalen-2-ol and 2-methoxynaphthalen-1-ol acetates (87% yield) was produced at rt. e 4-Methoxyphenyl acetate (23%, 2h ) was also isolated. f The reaction mixture was stirred at 50 °C for 24 h. …”

“… a Data taken from refs − . Arene (1.0 mmol) in AcOH (0.5 mL) was added to a suspension of NaNO 3 (2.2 mmol), TFA (0.5 mL), Ac 2 O (1.1 mmol) and AcOH (1.0 mL) at rt and the reaction mixture was stirred at rt for 14 h. …”