Efficient Synthesis of Diaryl Sulfides via Three Component Cross Coupling

doi:10.6023/cjoc202407024

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (4): 1283-1296.DOI: 10.6023/cjoc202407024 Previous Articles Next Articles

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三组分交叉偶联反应高效合成双芳基硫醚

刘梦琴^a, 陈贻庭^a, 张榉元^a, 周和烨^a, 秦涛^a^,^*(), 刘彬^a^,^b^,^*()

a 三峡大学材料与化工学院湖北宜昌 443002
b 湖北三峡实验室湖北宜昌 443007

收稿日期:2024-09-04 修回日期:2024-10-10 发布日期:2024-11-08
基金资助:
国家自然科学基金(22201158); 高等学校学科创新引智计划(111计划); 高等学校学科创新引智计划(D20015); 湖北省自然科学基金(2024AFB212); 湖北省自然科学基金(2024AFB152)

Efficient Synthesis of Diaryl Sulfides via Three Component Cross Coupling

Mengqin Liu^a, Yiting Chen^a, Juyuan Zhang^a, Heye Zhou^a, Tao Qin^a(), Bin Liu^a^,^b()

a College of Materials and Chemical Engineering, China Three Gorges University, Yichang, Hubei 443002
b Hubei Three Gorges Laboratory, Yichang, Hubei 443007

Received:2024-09-04 Revised:2024-10-10 Published:2024-11-08
Contact: * E-mail: qintao@ctgu.edu.cn; liubin1@ctgu.edu.cn
Supported by:
National Natural Science Foundation of China(22201158); Programme of Introducing Talents of Discipline to Universities (111 Project); Programme of Introducing Talents of Discipline to Universities(D20015); Hubei Provincial Natural Science Foundation(2024AFB212); Hubei Provincial Natural Science Foundation(2024AFB152)

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Abstract

Diaryl sulfides are found in drugs and natural products, yet their synthesis traditionally requires metal-catalyzed cross-coupling reactions, high temperatures, and the use of the air-sensitive and extremely odorous thiophenols. A novel transition-metal-free strategy for the synthesis of unsymmetric diaryl sulfides via a three-component cross-coupling of polyfluoro- arenes, diaryliodide salts and potassium thioacetate is reported. This approach enables the formation of a diverse array of unsymmetric diaryl thioethers through two successive electrophilic substitution reactions involving commercially available potassium thioacetate and two electron-deficient aromatic hydrocarbons, demonstrating broad substrate scope and functional group compatibility. Additionally, this strategy facilitates the synthesis of sulfones and sulfoxides via a one-pot oxidation reaction, thereby extending its applicability. Gram-scale reactions and derivatization experiments have shown excellent results, further proving the potential application value of this reaction. Mechanistic insights were elucidated through control, radical inhibition and intermediate capture experiments.

Key words: transition metal-free, polyfluoroarenes, diaryliodonium salts, diaryl sulfides

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Mengqin Liu, Yiting Chen, Juyuan Zhang, Heye Zhou, Tao Qin, Bin Liu. Efficient Synthesis of Diaryl Sulfides via Three Component Cross Coupling[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1283-1296.

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Fig. & Tab. 8

References 15

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Entry	Molar ratio of 1a/2/3a	2	Temp./℃	Solvent	Yield^b/% of 4a
1^c	1/1.5/2	2a	80	DMSO	Trace
2^c	1/1.5/2	2b	80	DMSO	42
3	1/1.5/2	2c	80	DMSO	69
4^d	1/1.5/2	2d	80	DMSO	56
5	1/1.5/2	2e	80	DMSO	55
6	1/1.5/2	2f	80	DMSO	43
7	1/1.5/2	2c	80	DMF	57
8	1/1.5/2	2c	80	Acetone	43
9	1/1.5/2	2c	80	THF	Trace
10	1/1.5/2	2c	80	CH₃CN	Trace
11	1/1.5/2	2c	80	Toluene	n.d.
12	1/1.5/2	2c	80	DCE	n.d.
13	1/1.5/2	2c	60	DMSO	58
14	1/1.5/2	2c	100	DMSO	73
15	1/2/2	2c	100	DMSO	82
16	1/2/1.5	2c	100	DMSO	61

Entry	Molar ratio of 1a/2/3a	2	Temp./℃	Solvent	Yield^b/% of 4a
1^c	1/1.5/2	2a	80	DMSO	Trace
2^c	1/1.5/2	2b	80	DMSO	42
3	1/1.5/2	2c	80	DMSO	69
4^d	1/1.5/2	2d	80	DMSO	56
5	1/1.5/2	2e	80	DMSO	55
6	1/1.5/2	2f	80	DMSO	43
7	1/1.5/2	2c	80	DMF	57
8	1/1.5/2	2c	80	Acetone	43
9	1/1.5/2	2c	80	THF	Trace
10	1/1.5/2	2c	80	CH₃CN	Trace
11	1/1.5/2	2c	80	Toluene	n.d.
12	1/1.5/2	2c	80	DCE	n.d.
13	1/1.5/2	2c	60	DMSO	58
14	1/1.5/2	2c	100	DMSO	73
15	1/2/2	2c	100	DMSO	82
16	1/2/1.5	2c	100	DMSO	61

三组分交叉偶联反应高效合成双芳基硫醚

Efficient Synthesis of Diaryl Sulfides via Three Component Cross Coupling

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