Electrochemical Oxidative C(sp3)—H Sulfonylation of Xanthenes with Sodium Sulfinates

doi:10.6023/cjoc202207012

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (1): 186-194.DOI: 10.6023/cjoc202207012 Previous Articles Next Articles

氧杂蒽与亚磺酸钠的电化学氧化C(sp³)—H磺酰化反应

危斌^†, 周子龙^†, 秦景灏^*(), 严泽宇, 郭嘉程, 雷澍, 谢叶香, 欧阳旋慧^*(), 宋仁杰^*()

南昌航空大学江西省持久性污染物控制与资源回收重点实验室南昌 330063

收稿日期:2022-07-05 修回日期:2022-07-29 发布日期:2022-09-15
通讯作者: 秦景灏, 欧阳旋慧, 宋仁杰
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(51878326); 国家自然科学基金(21861027); 国家自然科学基金(22161030); 国家自然科学基金(21901100); 江西省自然科学基金(20212ACB203007); 江西省自然科学基金(20204BCJ23010); 江西省自然科学基金(20202ACBL216017); 江西省自然科学基金(20212AEI91002); 江西省自然科学基金(20202ACB203002); 江西省教育厅自然科学基金(GJJ210906); 江西省教育厅自然科学基金(GJJ210909)

Electrochemical Oxidative C(sp³)—H Sulfonylation of Xanthenes with Sodium Sulfinates

Bin Wei^†, Zilong Zhou^†, Jinghao Qin(), Zeyu Yan, Jiacheng Guo, Shu Lei, Yexiang Xie, Xuanhui Ouyang(), Renjie Song()

Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063

Received:2022-07-05 Revised:2022-07-29 Published:2022-09-15
Contact: Jinghao Qin, Xuanhui Ouyang, Renjie Song
About author:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(51878326); National Natural Science Foundation of China(21861027); National Natural Science Foundation of China(22161030); National Natural Science Foundation of China(21901100); Natural Science Foundation of Jiangxi Province(20212ACB203007); Natural Science Foundation of Jiangxi Province(20204BCJ23010); Natural Science Foundation of Jiangxi Province(20202ACBL216017); Natural Science Foundation of Jiangxi Province(20212AEI91002); Natural Science Foundation of Jiangxi Province(20202ACB203002); Natural Science Foundation of Jiangxi Provincial Education Department(GJJ210906); Natural Science Foundation of Jiangxi Provincial Education Department(GJJ210909)

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Abstract

A direct electrochemical sulfonylation of C(sp³)—H bonds of xanthenes with sodium sulfinates was studied. A wide variety of 9-(arylsulfonyl)-9H-xanthenes and 9-(alkylsulfonyl)-9H-xanthenes were constructed in a single step at room temperature. This reaction proceeded through a radical pathway and a new C—S bond was formed under this electrochemical sulfonylation transformation. The significant advantages of this strategy include transition metal- and additional oxidant-free, mild reaction conditions, operational simplicity, broad substrate scope and excellent functional group tolerance.

Key words: electrooxidation, sulfonylation, xanthene, sodium sulfinate

Cite this article

Bin Wei, Zilong Zhou, Jinghao Qin, Zeyu Yan, Jiacheng Guo, Shu Lei, Yexiang Xie, Xuanhui Ouyang, Renjie Song. Electrochemical Oxidative C(sp³)—H Sulfonylation of Xanthenes with Sodium Sulfinates[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 186-194.

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References 10

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氧杂蒽与亚磺酸钠的电化学氧化C(sp³)—H磺酰化反应

Electrochemical Oxidative C(sp³)—H Sulfonylation of Xanthenes with Sodium Sulfinates

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Abstract

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References 10

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Entry	Variation from the standard conditions	Yield^b/%
1	None	71
2	ⁿBu₄NPF₆ instead of ⁿBu₄NBF₄	52
3	TBAI instead of ⁿBu₄NBF₄	41
4	TBAB instead of ⁿBu₄NBF₄	57
5	Pt(+)/C(–) instead of C(+)/Pt(–)	59
6	C(+)/C(–) instead of C(+)/Pt(–)	64
7	C(+)/RVC(–) instead of C(+)/Pt(–)	56
8	C(+)/Fe(–) instead of C(+)/Pt(–)	33
9	C(+)/Zn(–) instead of C(+)/Pt(–)	58
10	C(+)/Ni(–) instead of C(+)/Pt(–)	49
11	Without AcOH	Trace
12	HCOOH instead of AcOH	55
13	H₃PO₄ instead of AcOH	42
14	H₃BO₃ instead of AcOH	53
15	MsOH instead of AcOH	45
16	AcOH (1 equiv.)	56
17	AcOH (3 equiv.)	61
18	No electric current	0
19	5 mA instead of 10 mA, 3.5 h	60
20	15 mA instead of 10 mA, 2 h	51
21	CF₃CH₂OH instead of HFIP	38
22	CH₃CH₂OH instead of HFIP	Trace
23	MeOH instead of HFIP	42
24	MeCN instead of HFIP	52
25	ClCH₂CH₂Cl instead of HFIP	44
26	MeCN/HFIP (V∶V=1∶1, 5 mL)	40
27	ClCH₂CH₂Cl/HFIP (V∶V=1∶1, 5 mL)	45

氧杂蒽与亚磺酸钠的电化学氧化C(sp3)—H磺酰化反应