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钯催化下N-亚硝基导向的芳环上氨基邻位C(sp2)-H键的直接酰氧基化反应
  • ISSN号:0023-074X
  • 期刊名称:《科学通报》
  • 时间:0
  • 分类:O627.41[理学—有机化学;理学—化学]
  • 作者机构:[1]南京师范大学化学与材料科学学院,南京210097, [2]江苏省生物功能材料协同创新中心,南京210097, [3]江苏省资源循环与污染控制重点实验室,南京210097
  • 相关基金:国家自然科学基金(21272117)和江苏省优势学科建设工程资助
中文摘要:

以醋酸钯为催化剂,通过对芳环sp2碳氢键的活化,实现了一个高区域选择性的芳环上氨基邻位的直接酰氧基化反应.该反应具有良好的官能团兼容性,当苯环上有给电子基或一般吸电子基时反应均可发生.该方法具有反应条件温和、操作简单、条件易于控制、产率较高等优点.对可能的反应机理提出了建议.

英文摘要:

Transition metal-catalyzed direct C-H bond functionalization has been used in the construction of a variety of carbon-carbon and carbon-heteroatom bonds with features of step-economics and green chemistry primarily. By this strategy, a series of valuable polyfunctional compounds can be synthesized expediently. The efficient coordination of nitroso to transition metals made this group act as a favorable directing group to carry out the functionalization of inert C-H bond. N-Nitrosoanilines are also a class of very useful medicinal compounds and synthetic materials for the preparation of various nitrogen-containing compounds. In this paper, an efficient and highly regioselective direct ortho-acyloxylation of N-alkyl-N-nitrosoarylamines was developed. Under the catalysis of palladium, by the use of HOAc/Ac20 mixture as the AcO-source and solvent, and PhI(OAc)2 as the oxidant, the reaction gave acyloxylation products on ortho-position of N-alkyl-N-nitrosoarylamines with very high selectivity in moderate to good yields. The reaction conditions were optimized to be N-alkyl-N-nitrosoarylamines mixed with Pd(OAc)2 (10 tool%), and PhI(OAc)2 in HOAc/Ac20 (1: 1, v/v), under an air atmosphere at 70~C for 6 h. The reaction can tolerate a series of functional groups such as alkyl, alkoxyl, halogen and ester, etc. The mechanism for the reaction was proposed to be via a five-membered cyclopalladated intermediate which was formed by the coordination of nitroso to palladium, and a Pd(II)/Pd(IV) catalytic cycle was suggested in this transformation. The reaction could proceed under relatively mild reaction conditions, making the method highly applicable.

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期刊信息
  • 《科学通报》
  • 北大核心期刊(2011版)
  • 主管单位:中国科学院
  • 主办单位:中国科学院
  • 主编:周光召
  • 地址:北京东黄城根北街16号
  • 邮编:100717
  • 邮箱:csb@scichina.org
  • 电话:010-64036120 64012686
  • 国际标准刊号:ISSN:0023-074X
  • 国内统一刊号:ISSN:11-1784/N
  • 邮发代号:80-213
  • 获奖情况:
  • 首届国家期刊奖,中国期刊方阵“双高”期刊,第三届中国出版政府奖
  • 国内外数据库收录:
  • 美国化学文摘(网络版),美国数学评论(网络版),美国工程索引,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),中国北大核心期刊(2000版)
  • 被引量:81792