铜催化苯硼酸与苯并呋咱-1-氧化物的胺化反应

引用本文: 王曼曼, 李云云, 王芬, 李兴伟. 铜催化苯硼酸与苯并呋咱-1-氧化物的胺化反应[J]. 催化学报, 2017, 38(11): 1842-1850. doi: 10.1016/S1872-2067(17)62914-0 shu

Citation: Manman Wang, Yunyun Li, Fen Wang, Xingwei Li. Copper-catalyzed amination of phenylboronic acids with benzofurazan 1-oxides[J]. Chinese Journal of Catalysis, 2017, 38(11): 1842-1850. doi: 10.1016/S1872-2067(17)62914-0 shu

铜催化苯硼酸与苯并呋咱-1-氧化物的胺化反应

a 河南师范大学化学化工学院, 河南省精细化工绿色生产协同创新中心, 河南省有机功能分子和药物创新重点实验室, 河南新乡 453007;
b 中国科学院大连化学物理研究所, 辽宁大连 116023
基金项目:
国家自然科学基金（21525208，21472186）；河南师范大学研究基金（5101034011009）.

摘要: C-N键普遍存在于药物和有机功能分子中，传统构建C-N键的方法包括Goldberg反应、Buchwald-Hartwig偶联、Chan-Lam偶联和C-H键活化胺化.虽然这些方法都可以高效构建C-N键，但它们需要使用官能化的芳基底物、官能化的胺化试剂或在氧化条件下进行.理想的胺化反应应在氧化还原中性条件下进行，更为理想的则是在引入氨基的同时引入另外一个官能团.实现这个目标最直接的策略就是使用氮杂环，通过N-E （E=N或O）键的断裂，N原子和E原子可同时被引入.最近我们课题组利用氨茴内酐和氮杂苯并降冰片烯的C-H键活化反应成功实现了这种双官能团化.
尽管该法很有吸引力，但是要通过氮杂环的断裂实现双官能团化，需要发生非张力环的开环，这在热力学上是非常不利的.苯并呋咱-1-氧化物可以开环得到邻二硝基苯中间体.基于对胺化反应的兴趣，我们推测苯并呋咱1-氧化物可以作为一个胺化试剂实现苯硼酸的胺化.尽管亚硝基苯对芳基硼酸进行简单的胺化已经被报道，但需要化学计量的铜盐，或是引入还原剂.因此本文报道铜催化的苯硼酸的胺化反应，该反应以苯并呋咱1-氧化物为胺化试剂，在温和及氧化还原中性条件下成功实现了双官能团化.
本文共完成了31个不同官能团取代的硝基苯胺骨架结构的合成，反应均以中等到良好的收率得到目标产物，最高收率可达99%.为了增加反应的实用性，我们还进行了放大实验，实验表明，当苯并呋咱-1-氧化物的量由0.2 mmol放大至4 mmol时，反应仍能以较高的收率得到目标产物.此外，目标产物通过进一步的衍生化反应还可方便地转化为其他杂环类化合物.例如，在PPh3作用下，通过还原环化作用可生成吩嗪.在钯催化下可发生分子内碳氢键氧化反应得到咔唑类化合物.通过还原及重氮化反应还可方便地转化为苯并三唑.
总之，我们以苯并呋咱-1-氧化物为胺化试剂，在铜催化下成功实现了苯硼酸的胺化反应，合成了一系列双官能团化产物.该催化体系反应条件温和，底物适用范围广，对各种官能团具有很好的兼容性.

关键词:

English

Copper-catalyzed amination of phenylboronic acids with benzofurazan 1-oxides

a Henan Key Laboratory of Organic Functional Molecule and Drug Innovation, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, Henan, China;
b Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
Received Date: 26 June 2017
Revised Date: 07 August 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21525208 and 21472186) and Research Fund from Henan Normal University (5101034011009).

Abstract: CuCl/Phen can catalyze the C-N coupling between arylboronic acid and benzofurazan 1-oxide. This reaction occurred under mild and redox-neutral conditions with benzofurazan 1-oxide as an ami-nating reagent via ring scission, leading to a bifunctionalized aminonitrobenzene.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

铜催化苯硼酸与苯并呋咱-1-氧化物的胺化反应

English

Copper-catalyzed amination of phenylboronic acids with benzofurazan 1-oxides

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

铜催化苯硼酸与苯并呋咱-1-氧化物的胺化反应

English

Copper-catalyzed amination of phenylboronic acids with benzofurazan 1-oxides

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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