Citation: Rong Jian, Ni Chuanfa, Wang Yunze, Kuang Cuiwen, Gu Yucheng, Hu Jinbo. Radical Fluoroalkylation of Aryl Alkenes with Fluorinated Sulfones by Visible-Light Photoredox Catalysis[J]. Acta Chimica Sinica, ;2017, 75(1): 105-109. doi: 10.6023/A16080412 shu

Radical Fluoroalkylation of Aryl Alkenes with Fluorinated Sulfones by Visible-Light Photoredox Catalysis

Rong Jian ^a ,
Ni Chuanfa ^a ,
Wang Yunze ^a ,
Kuang Cuiwen ^a ,
Gu Yucheng ^b ,
Hu Jinbo ^a,*,,

a.
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
b.
Syngenta, Jealott's Hill International Research Centre Bracknell, Berkshire UK RG42 6EY

Corresponding author: Hu Jinbo, jinbohu@sioc.ac.cn
Received Date: 14 August 2016

Fund Project: the National Natural Science Foundation of China 21421002Shanghai Academic Research Leader Program 15XD1504400the Youth Innovation Promotion Association CAS 2014231the National Natural Science Foundation of China 21372246the National Natural Science Foundation of China 21472221973 Program 2015CB931900

Figures(3)

The incorporation of fluorine atoms or fluorinated moieties into organic molecules can often lead to significant changes of their physical, chemical, or biological properties. Consequently, fluorinated organic molecules are widely used in areas of pharmaceuticals, agrochemicals and materials. Traditional approaches for the incorporation of fluorinated moieties into organic molecules include nucleophilic, electrophilic, and radical pathways. Among them, radical fluoroalkylations under visible-light photoredox catalysis have attracted much attention because of the mild reaction conditions and broad functional-group tolerance. In our previous work, the radical fluoroalkylation of isocyanides with fluorinated sulfones as the fluoroalkyl radical precursors via R_f-SO₂Ar bond cleavage has been achieved under visible-light photoredox catalysis (Rong, J. et al. Angew. Chem., Int. Ed. 2016, 55, 2743). Herein, as a logical extension of our previous research, we report the radical fluoroalkylation of aryl alkenes with fluorinated sulfones as the practical fluoroalkyl radical precursors under visible-light photoredox catalysis. Various fluoroalkyl radicals, including trifluoromethyl (CF₃), difluoromethyl (HCF₂), 1, 1-difluoroethyl (CH₃CF₂) and (phenyl) difluoromethyl (PhCF₂) radicals, can be incorporated into styrene derivatives via this method, delivering the oxyfluoroalkylation products in 46%~93% yields. Typical procedures for this reaction are given as follows:to a Schlenk tube were added 2-vinylnaphthalene (1a) (0.20 mmol, 30.8 mg, 1.0 equiv.), trifluoromethyl 2-benzo[d]thiazolyl sulfone (2b) (0.24 mmol, 64.1 mg, 1.2 equiv.), fac-Ir (ppy)₃ (2.7 mg, 0.004 mmol, 2 mol%), H₂O (0.5 mL), and acetone (4.5 mL) sequentially. The resulting mixture was degassed with a freeze-pump-thaw procedure (3 times) and irradiated by a 6 W blue LED for 12 h. After the reaction completed, the mixture was extracted with Et₂O and dried over anhydrous MgSO₄. The organic solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel by using a 10:1 (V/V) mixture of petroleum ether/EtOAc as an eluent to provide the hydroxytrifluoromethylation product 3a (31.2 mg, 65% yield).
- visible-light photoredox catalysis,
- fluorinated sulfones,
- alkenes,
- difunctionalization,
- radical fluoroalkylation,
- trifluoromethylation,
- difluoromethylation
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