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

doi:10.6023/A16080412

Acta Chimica Sinica ›› 2017, Vol. 75 ›› Issue (1): 105-109.DOI: 10.6023/A16080412 Previous Articles Next Articles

Special Issue: 有机光化学

Article

可见光促进下氟烷基砜对芳基烯烃的自由基氟烷基化反应 2017 Awarded

荣健^a, 倪传法^a, 王云泽^a, 匡翠文^a, 顾玉诚^b, 胡金波^a

a 中国科学院上海有机化学研究所有机氟化学重点实验室上海 200032;
b Syngenta, Jealott's Hill International Research Centre Bracknell, Berkshire UK RG42 6EY

投稿日期:2016-08-14 修回日期:2016-09-07 发布日期:2016-09-18
通讯作者: 胡金波,E-mail:jinbohu@sioc.ac.cn;Tel.:021-54925174. E-mail:jinbohu@sioc.ac.cn
基金资助:
项目受973计划（2015CB931900）、国家自然科学基金（21372246，21421002，21472221）、上海市学术带头人计划（15XD1504400）、中国科学院青年创新促进会（2014231）与Syngenta博士生奖学金资助.

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

Received:2016-08-14 Revised:2016-09-07 Published:2016-09-18
Supported by:
Project supported by the 973 Program (2015CB931900), the National Natural Science Foundation of China (21372246, 21421002, 21472221), Shanghai Aca-demic Research Leader Program (15XD1504400), the Youth Innovation Promotion Association CAS (2014231), and a Syngenta Ph.D. Studentship.

1. Radical Fluoroalkylation of Aryl Alkenes with Fluorinated Sulfones by Visible-Light Photoredox Catalysis.PDF(1029KB)

Abstract

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).

Key words: visible-light photoredox catalysis, fluorinated sulfones, alkenes, difunctionalization, radical fluoroalkylation, trifluoromethylation, difluoromethylation

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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.

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可见光促进下氟烷基砜对芳基烯烃的自由基氟烷基化反应 2017 Awarded

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

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