Electrochemical Oxidative Thiocyanosulfonylation of Aryl Acetylenes

doi:10.6023/cjoc202209041

Abstract

Thiocyano and sulfonyl groups as important functional groups are widely existing in natural products, agrochemicals and medicines. They are also versatile synthetic intermediates that could be converted into various functionalities. There are limited reports on the synthesis of compounds that contain these two functional groups. A simple three-component thiocyanatosulfonylation of aryl acetylenes with sodium sulfinates and NH₄SCN through electrochemical oxidation to construct thiocyanated vinylsulfones has been established. The reaction employs easily accessible starting materials and features the characterization of external oxidant-free, mild reaction conditions, and high stereoselectivity. Moreover, this method enables two C—S bonds to be simultaneously formed in a one-step reaction.

Key words: alkyne, difunctionalization, electrochemistry, radical, thiocyanation, sulfonylation, green chemistry

Cite this article

Yu Zheng, Shencheng Qian, Pengcheng Xu, Binnan Zheng, Shenlin Huang. Electrochemical Oxidative Thiocyanosulfonylation of Aryl Acetylenes[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4275-4281.

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Entry	Variation from standard conditions	Yield^b/%
1	None	58
2	HFIP instead of TFE	Trace
3	No TFE or no H₂O	39, 0
4	KSCN instead of NH₄SCN	Trace
5	TsNHNH₂ instead of TsNa	Trace
6	TsNa (4.0 equiv.) or NH₄SCN (3.0 equiv.)	27, 41
7	No LiClO₄	38
8	5 mA instead of 8 mA	42
9	LiCl (2.0 equiv.) or ⁿBu₄NClO₄ (2.0 equiv.)	44, 22
10	MeCN/TFE/H₂O (V∶V∶V=9∶1∶1)	66
11	MeCN/TFE/H₂O (V∶V∶V=8∶1∶2)	47
12	C(+)/Ni(–)	55
13	No electric current	0

Entry	Variation from standard conditions	Yield^b/%
1	None	58
2	HFIP instead of TFE	Trace
3	No TFE or no H₂O	39, 0
4	KSCN instead of NH₄SCN	Trace
5	TsNHNH₂ instead of TsNa	Trace
6	TsNa (4.0 equiv.) or NH₄SCN (3.0 equiv.)	27, 41
7	No LiClO₄	38
8	5 mA instead of 8 mA	42
9	LiCl (2.0 equiv.) or ⁿBu₄NClO₄ (2.0 equiv.)	44, 22
10	MeCN/TFE/H₂O (V∶V∶V=9∶1∶1)	66
11	MeCN/TFE/H₂O (V∶V∶V=8∶1∶2)	47
12	C(+)/Ni(–)	55
13	No electric current	0

电化学氧化芳基端炔的硫氰化磺化反应