Synthesis of Pyrazolo(iso)quinoline Derivatives from Aryl Alkynes and N-Imine(iso)quinoline Ylides Catalyzed by Bisphosphonium Salt

doi:10.6023/cjoc202501005

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2876-2884.DOI: 10.6023/cjoc202501005 Previous Articles Next Articles

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双季鏻盐催化芳基炔烃与N-亚胺(异)喹啉叶立德合成吡唑并(异)喹啉衍生物

缪尹盛, 张磊, 陈建圻, 王丽丽^*(), 段征^*()

郑州大学化学学院国际磷化学实验室郑州 450001

收稿日期:2025-01-10 修回日期:2025-03-27 发布日期:2025-04-08
基金资助:
国家自然科学基金(22101262); 国家自然科学基金(22171245); 河南省科技攻关(242102230166)

Synthesis of Pyrazolo(iso)quinoline Derivatives from Aryl Alkynes and N-Imine(iso)quinoline Ylides Catalyzed by Bisphosphonium Salt

Yinsheng Miao, Lei Zhang, Jianqi Chen, Lili Wang^*(), Zheng Duan^*()

International Phosphorus Laboratory, College of Chemistry, Zhengzhou University, Zhengzhou 450001

Received:2025-01-10 Revised:2025-03-27 Published:2025-04-08
Contact: *E-mail:wanglili@zzu.edu.cn;duanzheng@zzu.edu.cn
Supported by:
National Natural Science Foundation of China(22101262); National Natural Science Foundation of China(22171245); Key Scientific and Technological Project of Henan Province(242102230166)

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Abstract

Recent studies have demonstrated that 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (Binap) based bisphosphonium salts Binap(OTf)₂ exhibit excellent catalytic performance in visible light photoredox catalysis, holding promise as a competitive class of visible-light catalysts. Binap(OTf)₂ was successfully utilized to catalyze the cyclization of aryl alkynes with N-imine(iso)quinoline ylides under blue light, addressing the limitations of substrate availability or accessibility in the current synthesis of β-aryl-substituted pyrazolo(iso)quinoline compounds. This approach provides a new strategy for the construction of pyrazolo(iso)quinoline compounds.

Key words: bisphosphonium salt, photoredox catalysis, N-imine(iso)quinolinium ylide, pyrazolo(iso)quinoline, aryl alkyne

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Yinsheng Miao, Lei Zhang, Jianqi Chen, Lili Wang, Zheng Duan. Synthesis of Pyrazolo(iso)quinoline Derivatives from Aryl Alkynes and N-Imine(iso)quinoline Ylides Catalyzed by Bisphosphonium Salt[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2876-2884.

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Fig. & Tab. 8

Figure 1. Organic photoredox catalysts

Scheme 1. Photoredox process catalyzed by bisphosphonium salt

Scheme 2. Methods for synthesizing pyrazolo(iso)quinolines

Table 1. Substrate range for the synthesis of pyrazolo[5,1-a]isoquinoline from N-imino(iso)quinoline ylides and aromatic alkynes catalyzed by PC5

Entry	1a/equiv.	Solvent	Additive	Yield/%
1	2.5	CHCl₃	—	16
2	2.5	MeCN	—	16
3	2.5	DCM	—	11
4	2.5	PhMe	—	N.D.
5	2.5	EtOH	—	N.D.
6	2.5	MeOH	—	Trace
7	2.5	THF	—	Trace
8	2.5	Acetone	—	Trace
9	1.5	CHCl₃	—	8
10	4	CHCl₃	—	17
11	2.5	CHCl₃	Na₂CO₃	16
12	2.5	CHCl₃	DDQ	21
13	2.5	CHCl₃	TCQ	73

Table 2. Optimization of conditions for the cyclization reactions of 1a and 3a catalyzed by PC5

Table 3. Substrate range for the synthesis of pyrazolo[1,5-a]quinoline from N-iminoquinoline ylides and aromatic alkynes catalyzed by PC5

Figure 2. Fluorescence quenching experiments

Scheme 3. Mechanism of PC5 catalyzed reaction between alkynes and N-iminoquinoline ylides to construct pyrazolo[1,5-a]quinoline derivatives

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双季鏻盐催化芳基炔烃与N-亚胺(异)喹啉叶立德合成吡唑并(异)喹啉衍生物

Synthesis of Pyrazolo(iso)quinoline Derivatives from Aryl Alkynes and N-Imine(iso)quinoline Ylides Catalyzed by Bisphosphonium Salt

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