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可见光照射下卤键引发的多氟烷基溴化物与邻二芳基异腈的自由基型插入反应
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:TQ423.21[化学工程]
  • 作者机构:[1]南京大学化学化工学院生命分析化学国家重点实验室,南京210023, [2]南京大学化学化工学院理论与计算化学研究所,南京210023
  • 相关基金:国家自然科学基金面上项目资助(Nos.21672098,21472084,21273102)
中文摘要:

报道了一种由卤键引发的自由基型双异腈插入反应.多氟烷基溴化物作为卤键的给体,有机碱作为卤键的受体.在可见光照射下,卤键复合物发生单电子转移过程生成多氟烷基自由基,被邻二芳基异腈捕获生成2-多氟烷基化喹喔啉衍生物.该反应在室温条件下进行,产率高,底物适用性广.反应的自由基属性可以通过EPR实验验证.2-多氟烷基化喹喔啉衍生物中3-位氢源可以通过氘代实验确定,实验显示氢源来自于有机碱和溶剂,而且溶剂是最主要的氢源.

英文摘要:

A halogen-bond-promoted double radical isocyanide insertion of o-diisocyanoarenes with perfluoroalkyl bromides is reported, in which perfluoroalkyl bromides as halogen bond donors and organic bases as halogen bond acceptors. Fluoroalkyl radicals can be generated by a visible-light-induced single electron transfer(SET) process. Fluoroalkyl radicals are trapped by o-diisocyanoarenes to give 2-fluoroalkylated quinoxaline derivatives. These reactions could be carried out under mild conditions with good chemical yields and broad substrate scope. A broad range of fluoroalkyl bromides with different functionalities could undergo this reaction to give the corresponding quinoxaline derivatives in good yields. A variety of o-diisocyanides could be fluoroalkylated to give quinoxalines under our established conditions. The radical nature of this reaction was confirmed by electron paramagnetic resonance(EPR) experiments using tert-butyl-α-phenylnitrone(PBN) as a spin trap. When PBN was introduced into the reaction mixture, a spectrum signal attributed to the spin adduct C8F17-PBN appeared as a triplet of doublets. Without light and amine, almost no signal was observed. These phenomena strongly suggested that the perfluoroalkyl radical was the key intermediate and the generation of the intermediate heavily relied on the presence of light and amine. A series of deuteration experiments were performed and these results suggested that both the amine and solvent could serve as the hydrogen source and solvent was the major source.

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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