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可见光促进的酰胺氮自由基参与的分子内氢胺化反应
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:O623.731[理学—有机化学;理学—化学]
  • 作者机构:f农药与化学生物学教育部重点实验室华中师范大学化学学院,武汉430079
  • 相关基金:国家自然科学基金(Nos.21272087,21472058,21472057,and 21232003); 武汉市青年科技晨光计划项目(No.2015070404010180)资助
中文摘要:

报道了可见光促进的邻烯基取代苯甲酰胺的分子内自由基氢胺化反应.在该反应中,通过脱质子光致电子转移策略实现了氮-氢键的直接催化活化来产生氮自由基,随后通过氮自由基与烯烃的加成来实现氢胺化反应.该反应以优异的收率合成了一系列具有潜在生理活性的3,4-二氢异喹啉酮衍生物.该反应体系利用有机染料催化剂Eosin Y Na作为光氧化还原催化剂、廉价易得的Na OH作为碱试剂、反应条件温和、操作简单、且官能团兼容性好.另外,该反应在放大量到克级规模、或者利用太阳光作为光源,均能以优异的收率得到相应目标化合物.因此,这类反应为3,4-二氢异喹啉酮的合成提供了一个简便有效的方法.

英文摘要:

The 3,4-dihydroisoquinolinones are a privileged class of heterocyclic motifs and widely found in numerous biologically active compounds. Thus, the development of more efficient and practical methods for their synthesis is highly desirable. Traditional methods are typically focused on transition-metal catalyzed C—H functionalization. Inspired by the recent process of the visible light photocatalytic generation and exploration of N-radicals in organic synthesis, our group in 2014 developed a visible light-induced photocatalytic strategy for direct conversion of the N—H bonds of β,γ-unsaturated hydrazones into N-centred radicals for the first time, and used them in intramolecular radical hydroamination, enabling efficient synthesis of 4,5-dihydropyrazole derivatives. By employing suitable additives or changing reaction parameters, we also successfully achieved highly regioselective 6-endo N-radical cyclization and oxyamination reactions based on N-centred radicals, providing the valuable 1,6-dihydropyradazines, pyrazolines, and pyridazines in good yields. In the hope of extending such N-radical-mediated heterocycle synthesis further, we reported a transition-metal free and visible light photocatalytic N-radical-based intramolecular hydroamination of benzamides. The reaction provides a practical and efficient approach to various biologically important 3,4-dihydroisoquinolinones with generally high yields. Importantly, the continuous flow reaction could significantly shorten the reaction time and still give rise to satisfactory yield. The sunlight irradiation reaction and gram-scale reaction also highlighted the potential synthetic utility of this method. A general procedure for the reaction is as follows: Eosin Y Na(6.21 mg, 0.009 mmol), Na OH(14.4 mg, 0.36 mmol), amide 1(0.3 mmol) were dissolved in Me OH(6.0 m L), then, the resulting mixture was degassed via a ‘freeze-pump-thaw' procedure(3 times). After that, the resulting mixture was stirred at a distance of ca. 5 cm from 3 W blue L

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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