钯催化的芳基C-H键三氟甲硫基化反应

doi:10.6023/A15030211

化学学报 ›› 2015, Vol. 73 ›› Issue (12): 1294-1297.DOI: 10.6023/A15030211 上一篇下一篇

所属专题：碳氢键官能团化

研究通讯

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).

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1. 钯催化的芳基C-H键三氟甲硫基化反应.PDF(697KB)

摘要/Abstract

报道了二价钯催化的高选择性芳基C-H键的三氟甲硫基化反应,其中稳定的三氟甲硫基苯胺2a作为三氟甲硫基试剂,醋酸钯作为催化剂,苯甲酰氯和醋酸银作为添加剂,反应在DMF中120℃条件下实现的.各种取代的吡啶都可以作为该反应的导向基团.反应中苯甲酰氯的添加对活化三氟甲硫基苯胺2a起着关键作用.该反应为合成邻位三氟甲硫基取代苯类衍生物提供了高效方便的方法.

关键词: 钯催化, C-H键活化, 三氟甲硫基化, 三氟甲硫基胺

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

引用此文

徐佳斌, 陈品红, 叶金星, 刘国生. 钯催化的芳基C-H键三氟甲硫基化反应[J]. 化学学报, 2015, 73(12): 1294-1297.

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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