Rh(III)催化基于胺化试剂极性翻转策略的定位基辅助芳烃C-H键胺化反应

doi:10.1016/S1872-2067(20)63587-2

催化学报 ›› 2020, Vol. 41 ›› Issue (11): 1723-1733.DOI: 10.1016/S1872-2067(20)63587-2

Rh(III)催化基于胺化试剂极性翻转策略的定位基辅助芳烃C-H键胺化反应

郑光范^a,c, 孙佳琼^a, 许有伟^c, 周旭凯^a, 高辉^b, 李兴伟^a,c

a 陕西师范大学化学化工学院, 胶体与界面化学教育部重点实验室, 陕西西安 710062;
b 广州医科大学药学院&第五附属医院, 分子靶向与临床药理学重点实验室, 广东广州 511436;
c 中国科学院大连化学物理研究所, 辽宁大连 116023

收稿日期:2020-02-27 修回日期:2020-03-30 出版日期:2020-11-18 发布日期:2020-08-15
通讯作者: 李兴伟
基金资助:
国家自然科学基金（21525208）；中国博士后基金（2019TQ0192，2019M653531，2019M663613）；中央高校基本科研业务费专项资金（GK201903028）和陕西师范大学.

Rhodium(III)-catalyzed chelation-assisted C-H imidation of arenes via umpolung of the imidating reagent

Guangfan Zheng^a,c, Jiaqiong Sun^a, Youwei Xu^c, Xukai Zhou^a, Hui Gao^b, Xingwei Li^a,c

a Key Laboratory of Applied Surface and Colloid Chemistry of MOE&School of Chemistry and Chemical Engineering Shaanxi Normal University(SNNU), Xi'an 710062, Shaanxi, China;
b Key Laboratory of Molecular Target and Clinical Pharmacology, School of Pharmaceutical Sciences&Fifth Affiliated Hospital, Guangzhou Medical University, Guangzhou 511436, Guangdong, China;
c Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2020-02-27 Revised:2020-03-30 Online:2020-11-18 Published:2020-08-15
Supported by:
We acknowledge financial support from NSFC (21525208), China Postdoctoral Science Foundation (2019TQ0192, 2019M653531, 2019M663613), and Fundamental Research Funds for the Central Universities (GK201903028) and SNNU.

摘要/Abstract

摘要： 芳胺类化合物广泛存在于农药、医药和生物活性分子中，因此发展芳胺类化合物新的合成方法受到有机合成工作者的广泛关注.Buchwald-Hartwig偶联，Chan-Lam胺化和Ullmann反应等的发展为芳胺类化合物的合成提供了重要方法.过渡金属催化的C-H键直接胺化反应因起始原料简单易得、高原子和步骤经济性等优势成为合成芳胺类化合物的重要方法.Cp^*Rh（III）/Ir（III）等催化的C-H键直接胺化反应有了快速的发展，合成了大量重要的芳胺类化合物，但是该类反应局限于应用乃春形式的氮源或预官能化的亲电性胺化试剂，基于亲核性氮源实现的C-H键胺化反应报道罕见.Su和Chang课题组实现了以TsNH₂为乃春前体的C-H键胺化反应.近期Yu课题组实现了铑催化当量碳酸银为氧化剂的二级胺类化合物氧化胺化反应.发展铑催化无需当量金属氧化剂的二级胺类化合物氧化胺化反应值得期待.我们认为，通过亲核性胺化试剂极性翻转策略将有望实现该类转化.高价碘化合物因环境友好和易于操作等优势在C-N键构建领域有着重要应用.我们认为，亲核性氮源与醋酸碘苯作用生成高价N-I（III）物种，可实现极性翻转，原位生成高活性亲电胺化试剂，进而在铑催化下实现芳基C-H键的氧化胺化反应.
本文选用糖精衍生物和双苯磺酰亚胺为亲核性氮源，商业易得、环境友好的醋酸碘苯为氧化剂，采用胺化试剂极性翻转策略，实现了定位基团辅助的芳基C-H键直接胺化反应.该策略底物适用范围宽泛，基团的兼容性良好，各种邻间对位取代和双取代的芳烃，萘环，噻吩和苯并呋喃，吲哚，咔唑等杂环芳烃均可以很好的发生反应.该反应可扩展至肟醚和吡啶，嘧啶，恶唑，吡唑和嘌呤等氮定位基.本文完成了45个不同官能团取代的芳胺类化合物的合成，反应均可以以中等到较高的产率得到目标产物，且该反应适用于克级规模制备.该反应条件温和，操作简单，为三级芳酰胺类化合物的合成提供了新方法.DFT计算结果表明C-N键的构建过程经历Rh（III）-Rh（V）-Rh（III）催化循环.

关键词: 芳胺, Rh(III)催化, C-H键氧化胺化, 高价碘试剂, 极性翻转

Abstract: Rh(III)-catalyzed, chelation-assisted oxidative C-H imidation of arenes with N-H imide have been realized using PhI(OAc)₂ as an oxidant. This transformation exhibits a broad substrate scope and tolerates various functional groups. The reaction proceeded via in situ generation of an iodine(III) imido. DFT calculations suggest that this oxidative imidaton system proceeds via a Rh(III)-Rh(V)-Rh(III) pathway.

Key words: Aryl amines, Rh(III) catalysis, Oxidative C-H imidation, Hypervalent iodine regent, Umpolung

郑光范, 孙佳琼, 许有伟, 周旭凯, 高辉, 李兴伟. Rh(III)催化基于胺化试剂极性翻转策略的定位基辅助芳烃C-H键胺化反应[J]. 催化学报, 2020, 41(11): 1723-1733.

Guangfan Zheng, Jiaqiong Sun, Youwei Xu, Xukai Zhou, Hui Gao, Xingwei Li. Rhodium(III)-catalyzed chelation-assisted C-H imidation of arenes via umpolung of the imidating reagent[J]. Chinese Journal of Catalysis, 2020, 41(11): 1723-1733.

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Rh(III)催化基于胺化试剂极性翻转策略的定位基辅助芳烃C-H键胺化反应

Rhodium(III)-catalyzed chelation-assisted C-H imidation of arenes via umpolung of the imidating reagent

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