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钯催化的芳基C—H键三氟甲硫基化反应
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:O627.42[理学—有机化学;理学—化学]
  • 作者机构:[1]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, [2]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
  • 相关基金:科技部(No.973-2015CB856600); 国家自然科学基金(Nos.21225210;21421091;21472219); 上海市科学技术委员会(No.12ZR1453400)资助
中文摘要:

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.

英文摘要:

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 m L glass tube, Pd(OAc)2(4.4 mg, 0.02 mmol), Ag OAc(33 mg, 0.2 mmol), Ph NHSCF3(50 μL, 0.5 mmol), substrate(0.2 mmol) and Ph COCl(58 μL, 0.5 mmol) were dissolved in dry DMF(1 m L) 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.

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期刊信息
  • 《化学学报》
  • 北大核心期刊(2014版)
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院上海有机化学研究所
  • 主编:周其林
  • 地址:上海市零陵路345号
  • 邮编:200032
  • 邮箱:hxxb@sioc.ac.cn
  • 电话:021-54925085
  • 国际标准刊号:ISSN:0567-7351
  • 国内统一刊号:ISSN:31-1320/O6
  • 邮发代号:4-209
  • 获奖情况:
  • 首届国家期刊奖,第二届国家期刊奖提名奖,中国期刊方阵“双高期刊”
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:28694