铑催化的硫代重氮氧化吲哚与吲哚的碳-氢键插入反应

doi:10.6023/cjoc202604022

有机化学 ›› 2026, Vol. 46 ›› Issue (10): 4016-4022.DOI: 10.6023/cjoc202604022 上一篇下一篇

研究论文

铑催化的硫代重氮氧化吲哚与吲哚的碳-氢键插入反应

崔效源^a^,^*(), 闫宇慧^a, 宋毅彤^a, 石艺^a, 李雪^a, 牛慧^a, 计从斌^b^,^*()

^a 晋中学院化学化工系山西晋中 030619
^b 上饶师范学院化学与环境科学学院江西上饶 334001

收稿日期:2026-04-15 修回日期:2026-05-21 发布日期:2026-07-06
基金资助:
晋中学院博士专项基金、大学生创新训练计划(20251419); 山西省新型多功能玻璃技术创新中心资助项目

Rhodium-Catalyzed C—H Bond Insertion Reaction of Diazothiooxindoles with Indoles

Xiaoyuan Cui^a^,^*(), Yuhui Yan^a, Yitong Song^a, Yi Shi^a, Xue Li^a, Hui Niu^a, Congbin Ji^b^,^*()

^a Department of Chemistry & Chemical Engineering, Jinzhong University, Jinzhong, Shanxi 030619
^b School of Chemistry and Environmental Sciences, Shangrao Normal College, Shangrao, Jiangxi 334001

Received:2026-04-15 Revised:2026-05-21 Published:2026-07-06
Contact:
^* E-mail: 19121715136@163.com;
jcbpxh521@163.com;
Supported by:
Jinzhong University Research Funds for Doctor, the Undergraduate Innovation Training Program(20251419); Shanxi Province New Multi-functional Glass Technology Innovation Center

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摘要/Abstract

硫代氧化吲哚是一类非常重要的杂环骨架, 广泛存在于天然产物和药物分子中. 以硫代重氮氧化吲哚和吲哚为原料, 在醋酸铑的催化下, 成功合成了硫代氧化吲哚衍生物. 该反应能够实现很好的区域选择性, 以吲哚C(3)位选择性碳-氢键插入产物为主. 同时, 对产物进行了初步生物活性测试, 针对胚胎细胞、黑色素瘤细胞、乳腺癌细胞及结肠癌细胞, 结果表明产物具有一定程度的抗肿瘤活性. 该反应具有条件简单和原子经济性高的特点.

关键词: 碳-氢键插入反应, 醋酸铑, 硫代氧化吲哚

Thiooxindole is a very important heterocyclic skeleton, which is widely found in natural products and pharmaceutical molecules. Thiooxindole derivatives were synthesized using diazothiooxindoles and indoles as raw materials under catalysis of rhodium acetate. This reaction delivers excellent regioselectivity, affording predominantly the C(3)-selective C—H insertion products. The activities of products were tested against NIH-3T3, B16-F10, 4T1, and HCT116. The results showed that the product exhibited a certain degree of antitumor activity. This reaction system features easy operation and high atom economy.

Key words: C—H bond insertion, rhodium acetate, thiooxindole

引用此文

崔效源, 闫宇慧, 宋毅彤, 石艺, 李雪, 牛慧, 计从斌. 铑催化的硫代重氮氧化吲哚与吲哚的碳-氢键插入反应[J]. 有机化学, 2026, 46(10): 4016-4022.

Xiaoyuan Cui, Yuhui Yan, Yitong Song, Yi Shi, Xue Li, Hui Niu, Congbin Ji. Rhodium-Catalyzed C—H Bond Insertion Reaction of Diazothiooxindoles with Indoles[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4016-4022.

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图/表 6

图1. 硫代氧化吲哚骨架的生物活性分子

Figure 1. Bioactive compounds with thiooxindole skeleton

图式1. 铑催化吲哚参与的碳-氢键插入反应

Scheme 1. Rhodium-catalyzed C—H bond insertion reaction of indoles

Entry	Catalyst	Solvent	T/℃	Yield^a/%
1	Ph₃PAuOTf	CH₂Cl₂	50	20
2	Fe(OTf)₃	CH₂Cl₂	50	10
3	AgOTf	CH₂Cl₂	50	8
4	Cu(OTf)₂	CH₂Cl₂	50	15
5	Rh₂(OAc)₄	CH₂Cl₂	50	72
6	Rh₂(OAc)₄	CHCl₃	50	70
7	Rh₂(OAc)₄	DCE	50	79
8	Rh₂(OAc)₄	Toluene	50	23
9	Rh₂(OAc)₄	EtOAc	50	28
10	Rh₂(OAc)₄	THF	50	37
11	Rh₂(OAc)₄	DCE	40	73
12	Rh₂(OAc)₄	DCE	60	75

表1. 反应条件的筛选和优化a

Table 1. Optimization of the reaction conditions

表2. 底物拓展

Table 2. Scope of substrate

图式2. 克级反应

Scheme 2. Gram-scale reaction

图式3. 可能的反应机理

Scheme 3. Possible reaction mechanism

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铑催化的硫代重氮氧化吲哚与吲哚的碳-氢键插入反应

Rhodium-Catalyzed C—H Bond Insertion Reaction of Diazothiooxindoles with Indoles

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