Desulfinative Cross-Coupling of Aryl Sodium Sulfinate with Aryl Sulfonium Salts

doi:10.6023/cjoc202509013

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (3): 1000-1007.DOI: 10.6023/cjoc202509013 Previous Articles Next Articles

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芳基亚磺酸钠与芳基硫鎓盐的脱硫交叉偶联反应

梁新宇^a^,^†, 米春春^a^,^†, 郭福军^a, 谢文斌^a^,^*(), 史钦钦^a^,^*(), 黄辉^a^,^b^,^*()

^a 中国科学院大学材料科学与光电技术学院北京 101408
^b 天津大学化工学院化学工程与低碳技术全国重点实验室化学工程与低碳技术全国重点实验室天津 300072

收稿日期:2025-09-09 修回日期:2025-11-06 发布日期:2025-12-09
作者简介:
†共同第一作者
基金资助:
国家自然科学基金(52222309); 国家自然科学基金(52173187); 国家自然科学基金(52303019); 国家自然科学基金(52450063); 北京自然科学基金(Z210017); 中国科学院战略性先导科技专项(XDB0520103); 中国科学院国际伙伴计划(124GJHZ2023079MI); 中国博士后科学基金(2024T170904); 中央高校基本科研业务费专项资金资助项目.

Desulfinative Cross-Coupling of Aryl Sodium Sulfinate with Aryl Sulfonium Salts

Xinyu Liang^a, Chunchun Mi^a, Fujun Guo^a, Wenbin Xie^a^,^*(), Qinqin Shi^a^,^*(), Hui Huang^a^,^b^,^*()

^a College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 101408
^b State Key Laboratory of Chemical Engineering and Low-Carbon Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072

Received:2025-09-09 Revised:2025-11-06 Published:2025-12-09
Contact: *E-mail: huihuang@tju.edu.cn; shiqinqin@ucas.ac.cn; xiewenbin@ucas.ac.cn
About author:
†These authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(52222309); National Natural Science Foundation of China(52173187); National Natural Science Foundation of China(52303019); National Natural Science Foundation of China(52450063); Beijing Natural Science Foundation(Z210017); Strategic Priority Research Program of Chinese Academy of Sciences(XDB0520103); International Partnership Program of Chinese Academy of Sciences(124GJHZ2023079MI); China Postdoctoral Science Foundation(2024T170904); Fundamental Research Funds for the Central Universities.

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Abstract

Transition-metal-catalyzed cross-coupling reactions represent a cornerstone strategy for C—C bond formation in organic synthesis. Herein, a Pd-catalyzed cross-coupling of aryl sodium sulfinates and aryl sulfonium salts via the interrupted Pummerer activation was developed. A variety of sodium sulfinates and aryl sulfonium salts were screened to show robustness of this method. Notably, two examples of late-stage functionalization of drugs exemplified potential utility in pharmaceutical synthesis.

Key words: transition metal catalysis, desulfinative coupling, C—H activation, post-modification of pharmaceuticals

Cite this article

Xinyu Liang, Chunchun Mi, Fujun Guo, Wenbin Xie, Qinqin Shi, Hui Huang. Desulfinative Cross-Coupling of Aryl Sodium Sulfinate with Aryl Sulfonium Salts[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1000-1007.

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References 34

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Entry	[Pd] (10 mol%)	Ligand (20 mol%)	Additive (2.0 equiv.)	Solvent	Temperature/℃	Yield^b/%
1	Pd(OAc)₂	PCy₃	K₂CO₃	1,4-dioxane	160	67
2	Pd(OAc)₂	P(t-Bu)₃H^＋BF₄^－	K₂CO₃	1,4-dioxane	160	42
3	Pd(PPh₃)₄	—	K₂CO₃	1,4-dioxane	160	72
4	Pd(OAc)₂	dtbpf	K₂CO₃	1,4-dioxane	160	63
5	Pd(OAc)₂	dppf	K₂CO₃	1,4-dioxane	160	61
6	Pd(PPh₃)₄	—	KOt-Bu	1,4-dioxane	160	16
7	Pd(PPh₃)₄	—	KF	1,4-dioxane	160	71
8	Pd(PPh₃)₄	—	Cs₂CO₃	1,4-dioxane	160	16
9	Pd(PPh₃)₄	—	AgOAc	1,4-dioxane	160	68
10	Pd(PPh₃)₄	—	Ag₂CO₃	1,4-dioxane	160	78 (72)^c
11	Pd(PPh₃)₄	—	Ag₂CO₃	1,4-dioxane	110	31
12	Pd(PPh₃)₄	—	Ag₂CO₃	DMSO	160	72

Entry	[Pd] (10 mol%)	Ligand (20 mol%)	Additive (2.0 equiv.)	Solvent	Temperature/℃	Yield^b/%
1	Pd(OAc)₂	PCy₃	K₂CO₃	1,4-dioxane	160	67
2	Pd(OAc)₂	P(t-Bu)₃H^＋BF₄^－	K₂CO₃	1,4-dioxane	160	42
3	Pd(PPh₃)₄	—	K₂CO₃	1,4-dioxane	160	72
4	Pd(OAc)₂	dtbpf	K₂CO₃	1,4-dioxane	160	63
5	Pd(OAc)₂	dppf	K₂CO₃	1,4-dioxane	160	61
6	Pd(PPh₃)₄	—	KOt-Bu	1,4-dioxane	160	16
7	Pd(PPh₃)₄	—	KF	1,4-dioxane	160	71
8	Pd(PPh₃)₄	—	Cs₂CO₃	1,4-dioxane	160	16
9	Pd(PPh₃)₄	—	AgOAc	1,4-dioxane	160	68
10	Pd(PPh₃)₄	—	Ag₂CO₃	1,4-dioxane	160	78 (72)^c
11	Pd(PPh₃)₄	—	Ag₂CO₃	1,4-dioxane	110	31
12	Pd(PPh₃)₄	—	Ag₂CO₃	DMSO	160	72

芳基亚磺酸钠与芳基硫鎓盐的脱硫交叉偶联反应

Desulfinative Cross-Coupling of Aryl Sodium Sulfinate with Aryl Sulfonium Salts

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Scope of aryl electrophiles

Scope of aryl nucleophiles

Scope of aryl electrophiles

Scope of aryl nucleophiles