Silver-Catalyzed Tandem Decarboxylative Cyclization of 2,2-Difluoro-2-(phenylthio)acetic Acids with 2-Aryl-N-acrylamide Indoles

doi:10.6023/cjoc202507011

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (1): 118-127.DOI: 10.6023/cjoc202507011 Previous Articles Next Articles

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银催化(2,2-二氟-2)-苯硫基乙酸和2-芳基-N-丙烯酰胺吲哚的串联脱羧环化反应

刘佳乐^a, 唐裕才^a^,^*(), 印丘梅^a, 黄嘉明^a, 邓世强^a, 夏伟铭^a, 蒋洁^a, 王祖利^b

^a 湖南文理学院化学与材料工程学院电镀废水回用技术湖南省工程研究中心湖南常德 415000
^b 南京林业大学化学工程学院南京 210037

收稿日期:2025-07-09 修回日期:2025-08-24 发布日期:2025-09-23
通讯作者: 唐裕才
基金资助:
湖南省教育厅优秀青年基金(23B0650); 湖南文理学院重点项目(24ZZ02); 常德市科技创新指导性计划(2025ZD124)

Silver-Catalyzed Tandem Decarboxylative Cyclization of 2,2-Difluoro-2-(phenylthio)acetic Acids with 2-Aryl-N-acrylamide Indoles

Liu Jiale^a, Tang Yucai^a^,^*(), Yin Qiumei^a, Huang Jiaming^a, Deng Shiqiang^a, Xia Weiming^a, Jiang Jie^a, Wang Zu-Li^b

^a College of Chemistry and Materials Engineering, Hunan Province Engineering Research Center of Electroplating Wastewater Reuse Technology, Hunan University of Arts and Science, Changde, Hunan 415000
^b School of Chemical Engineering, Nanjing Forestry University, Nanjing 210037

Received:2025-07-09 Revised:2025-08-24 Published:2025-09-23
Contact: Tang Yucai
Supported by:
Scientific Research Foundation of Hunan Provincial Education Department(23B0650); Key Research Project of Hunan University of Arts and Sciences(24ZZ02); Technology Innovation and Development Guidance Program of Changde(2025ZD124)

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Abstract

The introduction of SCF₂ motif into organic molecules would increases the bioactivity signiﬁcantly. A silver-cata- lyzed tandem decarboxylative cyclization of 2,2-difluoro-2-(phenylthio)acetic acids with 2-aryl-N-acrylamide indoles is described, furnishing 28 examples of SCF₂-substituted indolo[2,1-a]isoquinoline derivatives in moderate to good yields. Mechanistic studies reveal that a radical pathway is proposed in this transformation.

Key words: silver, decarboxylation, thiodifluoromethylation, indolo[2,1-a]isoquinoline derivatives

Cite this article

Liu Jiale, Tang Yucai, Yin Qiumei, Huang Jiaming, Deng Shiqiang, Xia Weiming, Jiang Jie, Wang Zu-Li. Silver-Catalyzed Tandem Decarboxylative Cyclization of 2,2-Difluoro-2-(phenylthio)acetic Acids with 2-Aryl-N-acrylamide Indoles[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 118-127.

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References 20

[1]	(a) Müller K.; Faeh C.; Diederich F. Science 2007, 317, 1881.
	(b) Hagmann W. K. J. Med. Chem. 2008, 51, 4359.
	(c) O’Hagan, D. Chem. Soc. Rev. 2008, 37, 308.
	(d) Z Purser, S.; Moore P. R.; Swallow S.; Gouverneur V. Chem. Soc. Rev. 2008, 37, 320.
[2]	(a) Erickson J. A.; McLoughlin J. I. J. Org. Chem. 1995, 60, 1626.
	(b) Aráoz R.; Anhalt E.; René L.; Badet-Denisot M.-A.; Courvalin P.; Badet B. Biochemistry 2000, 39, 15971.
	(c) Romanenko V. D.; Kukhar V. P. Chem. Rev. 2006, 106, 3868.
	(d) Liu C.-H.; Zhang Z.-W.; Zhao Z.-J.; Jiang J.; Yang Z.; Wang Z.-L.; He W.-M. J. Org. Chem. 2025, 90, 11982.
	(e) Peng Q.-H.; Li N.-B.; Hou J.-C.; He C.-J.; Yang Y.-X.; Zhuang C.-L.; Ou L.-J.; Yuan M.; He W.-M. Chin. Chem. Lett. 2025, 36, 111402.
	(f) Peng Q.-H.; Jiang J.; Liao Z.-H.; Wu Z.-L.; Ou L.-J.; Dai H.; Peng J.; He W.-M. ACS Sustainable Chem. Eng. 2025, 13, 10971.
[3]	Boyer J.; Arnoult E.; Médebielle M.; Guillemont J.; Unge J.; Jochmans D. J. Med. Chem. 2011, 54, 7974.
[4]	(a) Ni C.; Hu M.; Hu J. Chem. Rev. 2015, 115, 765.
	(b) Xu X. H.; Matsuzaki K.; Shibata N. Chem. Rev. 2015, 115, 731.
[5]	(a) Burkholder C. R.; Dolbier W. R., Jr.; Médebielle M. J. Fluorine Chem. 2001, 109, 39.
	(b) Guidotti J.; Metz F.; Tordeux M.; Wakselman C. Synlett 2004, 1759.
	(c) Wu Y.-M.; Li Y.; Deng J. J. Fluorine Chem. 2006, 127, 223.
	(d) Aikawa K.; Maruyama K.; Nitta J.; Hashimoto R.; Mikami K. Org. Lett. 2016, 18, 3354.
	(e) Geri J. B.; Wolfe M. M. W.; Szymczak N. K. J. Am. Chem. Soc. 2018, 140, 9404.
	(f) Xiao P.; Ni C.; Miao W.; Zhou M.; Hu J.; Chen D.; Hu J. J. Org. Chem. 2019, 84, 8345.
[6]	Choi Y.; Yu C.; Kim J. S.; Cho E. J. Org. Lett. 2016, 18, 3246.
[7]	(a) Shi G.; Shao C.; Pan S.; Yu J.; Zhang Y. Org. Lett. 2015, 17, 38.
	(b) Lin J.; Li Z.; Kan J.; Huang S.; Su W.; Li Y. Nat. Commun. 2017, 8, 14353.
	(c) Khrizanforov M. N.; Fedorenko S. V.; Mustafina A. R.; Kholin K. V.; Nizameev I. R.; Strekalova S. O.; Grinenko V. V.; Gryaznova T. V.; Zairov R. R.; Mazzaro R.; Morandi V.; Vomiero A.; Budnikova Y. H. Dalton Trans. 2018, 47, 9608.
[8]	(a) Tung T. T.; Christensen S. B.; Nielsen J. Chem.-Eur. J. 2017, 23, 18125.
	(b) Genovino J.; Lian Y.; Zhang Y.; Hope T. O.; Juneau A.; Gagné Y.; Ingle G.; Frenette M. Org. Lett. 2018, 20, 3229.
[9]	(a) Hong G.; Yuan J.; Fu J.; Pan G.; Wang Z.; Yang L.; Xiao Y.; Mao P.; Zhang X. Org. Chem. Front. 2019, 6, 1173.
	(b) Xie X.; Zhang Y.; Hao J.; Wan W. Org. Biomol. Chem. 2020, 18, 400.
	(c) Gao Y.; Zhao L.; Xiang T.; Li P.; Wang L. RSC Adv. 2020, 10, 10559.
	(d) Zhao F.; Guo S.; Zhang Y.; Sun T.; Yang B.; Ye Y.; Sun K. Org. Chem. Front. 2021, 8, 6895.
[10]	Zhu X.; Huang Y.; Xu X.; Qing F. Org. Lett. 2020, 22, 5451.
[11]	(a) Singh S.; Pathak N.; Fatima E.; Negi A. S. Eur. J. Med. Chem. 2021, 226, 113839.
	(b) Bhadra K.; Kumar G. S. Med. Res. Rev. 2011, 31, 821.
	(c) Plazas E.; Avila M M. C.; Muñoz D. R.; Cuca S L. E.; Cuca S. L. E. Pharmacol. Res. 2022, 177, 106126.
	(d) Tsyrenova B.; Khrustalev V.; Nenajdenko V. J. Org. Chem. 2020, 85, 7024.
	(e) Yi R.; He W. Chin. J. Org. Chem. 2023, 43, 2985 (in Chinese).
	(易荣楠, 何卫民, 有机化学, 2023, 43, 2985.)
	(f) Li C.; Wang Y.; Wu S.; Zhuang W.; Huang Z.; Zhou L.; Li Y.; Chen M.; You J. Org. Lett. 2022, 24, 175.
[12]	(a) Lu Y.-H.; Mu S.-Y.; Jiang J.; Zhou M.-H.; Wu C.; Ji H.-T.; He W.-M. ChemSusChem 2023, 16, e202300523.
	(b) Lu Y.-H.; Wu C.; Hou J.-C.; Wu Z.-L.; Zhou M.-H.; Huang X.-J.; He W.-M. ACS Catal. 2023, 13, 13071.
	(c) Song H.-Y.; Jiang J.; Wu C.; Hou J.-C.; Lu Y.-H.; Wang K.-L.; Yang T.-B.; He W.-M. Green Chem. 2023, 25, 3292.
	(d) Ji H.-T.; Wang K.-L.; Ouyang W.-T.; Luo Q.-X.; Li H.-X.; He W.-M. Green Chem. 2023, 25, 7983.
	(e) Zeng F.; Sun K.; Chen X.; Yuan X.; He S.; Liu Y.; Peng Y.; Qu L.; Lv Q.; Yu B. Adv. Synth. Catal. 2019, 361, 5176.
[13]	Wang B.; Zou L.; Wang L.; Sun M.; Li P. Chin. Chem. Lett. 2021, 32, 1229.
[14]	(a) Yu W.-Q.; Xiong B.-Q.; Zhong L.-J.; Liu Y. Org. Biomol. Chem. 2022, 20, 9659.
	(b) Zhang D.-L.; Zhu Z.-Q.; Xie Z.-B.; Zhang X.-P.; Le Z.-G. New J. Chem. 2023, 47, 18354.
[15]	(a) Zhai S.; Qiu S.; Yang S.; Hua B.; Niu Y.; Han C.; Yu Y.; Li Y.; Zhai H. Chin. Chem. Lett. 2022, 33, 276.
	(b) Shen Z.-J.; Huang B.; Ma N.; Yao L.; Yang C.; Guo L.; Xia W. Adv. Synth. Catal. 2021, 363, 1944.
[16]	(a) Hu X.-Y.; Xu H.-F.; Chen Q.; Pan Y.-L.; Chen J.-Z. Org. Biomol. Chem. 2021, 19, 10376.
	(b) Wei Y.-L.; Chen J.-Q.; Sun B.; Xu P.-F. Chem. Commun. 2019, 55, 5922.
[17]	Cui H.; Ni C.; Zhang C. J. Org. Chem. 2021, 86, 15835.
[18]	Zhang J.-R.; Liu H.-Y.; Fan T.; Chen Y.-Y.; Xu Y.-L. Adv. Synth. Catal. 2021, 363, 497.
[19]	(a) Luo Y.; Tian T.; Nishihara Y.; Lv L.; Li Z. Chem. Commun. 2021, 57, 9276.
	(b) Jiang S.; Xiao Y.-T.; Wu Y.-C.; Luo S.-Z.; Song R.-J.; Li J.-H. Org. Biomol. Chem. 2020, 18, 4843.
[20]	Tang Y.; Dai K.; Xiang X.; Yang Y.; Li M. Org. Biomol. Chem. 2022, 20, 5704.

Entry	Catalyst	Oxidant	Solvent	Yield^b/%
1	Ag₂CO₃	K₂S₂O₈	CH₃CN/H₂O	50
2	Ag₂SO₄	K₂S₂O₈	CH₃CN/H₂O	57
3	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	73
4	AgNO₃	K₂S₂O₈	DMSO/H₂O	10
5	AgNO₃	K₂S₂O₈	DMF/H₂O	Trace
6	AgNO₃	K₂S₂O₈	1,4-Dioxane/H₂O	43
7	AgNO₃	K₂S₂O₈	CH₃CN	0
8^c	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	74
9^d	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	68
10	AgNO₃	(NH₄)₂S₂O₈	CH₃CN/H₂O	65
11	AgNO₃	Na₂S₂O₈	CH₃CN/H₂O	57
12^e	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	0

Entry	Catalyst	Oxidant	Solvent	Yield^b/%
1	Ag₂CO₃	K₂S₂O₈	CH₃CN/H₂O	50
2	Ag₂SO₄	K₂S₂O₈	CH₃CN/H₂O	57
3	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	73
4	AgNO₃	K₂S₂O₈	DMSO/H₂O	10
5	AgNO₃	K₂S₂O₈	DMF/H₂O	Trace
6	AgNO₃	K₂S₂O₈	1,4-Dioxane/H₂O	43
7	AgNO₃	K₂S₂O₈	CH₃CN	0
8^c	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	74
9^d	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	68
10	AgNO₃	(NH₄)₂S₂O₈	CH₃CN/H₂O	65
11	AgNO₃	Na₂S₂O₈	CH₃CN/H₂O	57
12^e	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	0

银催化(2,2-二氟-2)-苯硫基乙酸和2-芳基-N-丙烯酰胺吲哚的串联脱羧环化反应

Silver-Catalyzed Tandem Decarboxylative Cyclization of 2,2-Difluoro-2-(phenylthio)acetic Acids with 2-Aryl-N-acrylamide Indoles

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