电化学氧化芳基端炔的硫氰化磺化反应

doi:10.6023/cjoc202209041

摘要/Abstract

硫氰基和磺酰基作为重要的官能团, 广泛存在于天然产物、农药和药物中, 同时它们作为合成中间体可以转化为其它多种官能团. 到目前为止, 合成兼具硫氰基和磺酰基这两类官能团的化合物的研究较少. 报道了一种简单的芳基端炔、亚磺酸钠和硫氰酸铵电化学氧化三组反应, 合成了一类硫氰代烯基砜类化合物. 该反应利用廉价易得的原料, 并具有无需外源氧化剂、反应条件温和及立体选择性高等特点. 此外, 该方法实现了一步反应中两个C—S键的同时构建.

关键词: 炔烃, 双官能团化, 电化学, 自由基, 硫氰化, 磺化, 绿色化学

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

引用此文

郑煜, 钱沈城, 徐鹏程, 郑斌南, 黄申林. 电化学氧化芳基端炔的硫氰化磺化反应[J]. 有机化学, 2022, 42(12): 4275-4281.

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