Rh-Catalyzed C—H Functionalization Reaction between 3-Diazoindolin-2-imines and Pyrazolones for the Construction of 3-Pyrazolyl Indoles

doi:10.6023/cjoc202211008

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (7): 2519-2527.DOI: 10.6023/cjoc202211008 Previous Articles Next Articles

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铑催化3-重氮吲哚-2-亚胺与吡唑啉酮的C—H官能团化反应制备3-吡唑基吲哚

许晓萍, 张翼飞, 莫小渝, 江俊^*()

广西大学化学化工学院南宁 530004

收稿日期:2022-11-08 修回日期:2023-01-17 发布日期:2023-02-14
通讯作者: 江俊
基金资助:
国家自然科学基金(22161005); 广西省自然科学基金(2021GXNSFDA075005); 中国科学院大连化学物理研究所分子反应动力学国家重点实验室开放基金(SKLMRD-K202106)

Rh-Catalyzed C—H Functionalization Reaction between 3-Diazoindolin-2-imines and Pyrazolones for the Construction of 3-Pyrazolyl Indoles

Xiaoping Xu, Yifei Zhang, Xiaoyu Mo, Jun Jiang()

School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004

Received:2022-11-08 Revised:2023-01-17 Published:2023-02-14
Contact: Jun Jiang
Supported by:
National Natural Science Foundation of China(22161005); Natural Science Foundation of Guangxi Province(2021GXNSFDA075005); Open Fund of the State key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics, Chinese Academy of Sciences(SKLMRD-K202106)

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Abstract

A highly efficient C—H functionalization reaction of α-imino carbenes and pyrazolones in the presence of Rh₂(OAc)₄ has been reported. This methodology provides a rapid and straightforward approach toward a variety of structurally diverse 3-pyrazolyl indoles by C—C bond formation in moderate to excellent yields with good functional group tolerance.

Key words: diazo compounds, metal carbenes, C—H functionalization, pyrazolones

Cite this article

Xiaoping Xu, Yifei Zhang, Xiaoyu Mo, Jun Jiang. Rh-Catalyzed C—H Functionalization Reaction between 3-Diazoindolin-2-imines and Pyrazolones for the Construction of 3-Pyrazolyl Indoles[J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2519-2527.

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Fig. & Tab. 8

Figure 1. Pharmacologically active 3-pyrazolyl indoles

Scheme 1. Strategies for the synthesis of 3-heterocyclic indoles via 3-diazoindolin-2-imines

Entry	Catalyst	Solvent	Temp./℃	Yield^b/%
1	Pd₂(OAc)₄	DCE	70	0
2	AgNO₃	DCE	70	0
3	Cu₂O	DCE	70	70
4	Rh₂(Oct)₄	DCE	70	86
5	Rh₂(OAc)₄	DCE	70	92
6	Rh₂(OAc)₄	CHCl₃	70	56
7	Rh₂(OAc)₄	EA	70	55
8	Rh₂(OAc)₄	Toluene	70	49
9	Rh₂(OAc)₄	DCE	rt	Trace
10	—	DCE	70	0
11^c	Rh₂(OAc)₄	DCE	70	98

Table 1. Optimization of the reaction conditionsa

Figure 2. X-ray structure of 3a

Table 2. Scope of 3-diazoindolin-2-iminesa,b

Table 3. Scope of pyrazolonesa,b

Scheme 2. Gram-scale reaction of 1a and 2a

Scheme 3. A plausible mechanism of C—H functionalization of α-imino rhodium carbene

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铑催化3-重氮吲哚-2-亚胺与吡唑啉酮的C—H官能团化反应制备3-吡唑基吲哚

Rh-Catalyzed C—H Functionalization Reaction between 3-Diazoindolin-2-imines and Pyrazolones for the Construction of 3-Pyrazolyl Indoles

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