Palladium-Catalyzed Trifluoromethylthiolation of Arenes via C-H Activation

doi:10.6023/A15030211

Acta Chimica Sinica ›› 2015, Vol. 73 ›› Issue (12): 1294-1297.DOI: 10.6023/A15030211 Previous Articles Next Articles

Special Issue: 碳氢键官能团化

Communication

钯催化的芳基C-H键三氟甲硫基化反应 2017 Awarded

徐佳斌^a, 陈品红^b, 叶金星^a, 刘国生^b

a 制药工程与过程化学研究中心华东理工大学药学院上海 200237;
b 金属有机化学国家重点实验室中国科学院上海有机化学研究所上海 200032

投稿日期:2015-03-27 发布日期:2015-05-15
通讯作者: 叶金星, 刘国生 E-mail:yejx@ecust.edu.cn;gliu@mail.sioc.ac.cn
基金资助:
项目受科技部(No.973-2015CB856600)、国家自然科学基金(Nos.21225210,21421091,21472219)和上海市科学技术委员会(No.12ZR1453400)资助.

Palladium-Catalyzed Trifluoromethylthiolation of Arenes via C-H Activation

Xu Jiabin^a, Chen Pinhong^b, Ye Jinxing^a, Liu Guosheng^b

a Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237;
b State Key Laboratory of Organometallics Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032

Received:2015-03-27 Published:2015-05-15
Supported by:
Project supported by the National Basic Research Program of China(No. 973-2015CB856600), the National Natural Science Foundation of China(Nos. 21225210, 21421091, 21472219) and Science Technology Commission of the Shanghai Municipality(No. 12ZR1453400).

1. Palladium-Catalyzed Trifluoromethylthiolation of Arenes via C-H Activation.PDF(697KB)

Abstract

Fluorinated organic compounds are widely used as pharmaceuticals, agrochemicals and materials. Among them, the trifluoromethylthio(-SCF₃) compounds has attracted much attention owning to its strong electron-withdrawing nature and high lipophilicity. Therefore, the development of new trifluoromethylthiolation methods has attracted great interest in synthetic organic chemistry. Traditional approaches for the synthesis of trifluoromethylthiolated arenes include halogen-fluorine exchange and the trifluoromethylation of sulfur-containing compounds such as disulfides, thiols, which suffer from poor functional compatibility and yield. Recent progress on the transition metal-catalyzed directing trifluoromethylthiolation using SCF₃ reagents provided an efficient approach to the target. Herein, we reported a Pd(II)-catalyzed highly selective C-H trifluoromethylthiolation of arenes. Different type of pyridines could be used as efficient directing groups for this reaction. In this reaction, benzoyl chloride was found to be crucial to activate the trifluoromethanesulfanamide 2a. It provides an efficient way for the synthesis of ortho-SCF₃ substituted arenes in high yields. A representative procedure for this reaction is as following:To a 10 mL glass tube, Pd(OAc)₂(4.4 mg, 0.02 mmol), AgOAc(33 mg, 0.2 mmol), PhNHSCF₃(50μL, 0.5 mmol), substrate(0.2 mmol) and PhCOCl(58μL, 0.5 mmol) were dissolved in dry DMF(1 mL) under N₂ atmosphere. The tube was sealed and the mixture was stirred at 120℃ for 12 h, and then cooled to room temperature. The mixture was concentrated and purified by column chromatography on silica gel with a gradient eluent of petroleum ether and ethyl acetate(range from 15:1 to 4:1) to provide the products in 62%~91% yields.

Key words: palladium-catalyzed, C-H activation, trifluoromethylthiolation, trifluoromethanesulfanamide

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Xu Jiabin, Chen Pinhong, Ye Jinxing, Liu Guosheng. Palladium-Catalyzed Trifluoromethylthiolation of Arenes via C-H Activation[J]. Acta Chimica Sinica, 2015, 73(12): 1294-1297.

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钯催化的芳基C-H键三氟甲硫基化反应 2017 Awarded

Palladium-Catalyzed Trifluoromethylthiolation of Arenes via C-H Activation

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