电化学氧化三氟甲基亚磺酸钠与α-羰基二硫缩烯酮的三氟甲基化反应

doi:10.6023/cjoc202112024

摘要/Abstract

报道了一种无过渡金属催化剂、外加化学氧化剂的条件下, 电化学氧化三氟甲基亚磺酸钠与α-羰基二硫缩烯酮的高效三氟甲基化反应. 该方法具有反应条件温和与较好的官能团兼容性的优点. 相关的机理实验表明该反应是通过自由基机理进行的.

关键词: 电化学, 三氟甲基化, α-羰基二硫缩烯酮, 自由基, 绿色化学

An efficient electrochemical oxidative trifluoromethylation of α-oxoketene dithioacetals with CF₃SO₂Na is developed without the usage of transition-metal catalysts and external oxidants. This protocol features mild reaction conditions and wide functionality tolerance. Mechanistic insights indicate that the reaction proceeded via radical mechanism.

Key words: electrochemical, trifluoromethylation, α-oxoketene dithioacetals, radical, green chemistry

引用此文

顾清云, 程振凤, 曾小宝. 电化学氧化三氟甲基亚磺酸钠与α-羰基二硫缩烯酮的三氟甲基化反应[J]. 有机化学, 2022, 42(5): 1537-1544.

Qingyun Gu, Zhenfeng Cheng, Xiaobao Zeng. Electrochemical Oxidative Trifluoromethylation of α-Oxoketene Ketene Dithioacetals with CF₃SO₂Na[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1537-1544.

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Entry	Variation from the standard conditions	Yield^b/%
1	None	77
2	C felt (+) \| C felt(–) Instead of C felt (+) \| Fe (–)	Trace
3	C felt (+) \| Ni felt(–) Instead of C felt (+) \| Fe (–)	62
4	n-Bu₄NPF₆instead of n-Bu₄NClO₄	74
5	n-Bu₄NBF₄instead of n-Bu₄NClO₄	71
6	Without electrolyte	61
7	DCE instead of MeCN	Trace
8	DMF instead of MeCN	Trace
9	AcOH instead of MeCN	52
10	Without H₂O	60
11	H₂O (20 equiv.)	75
12	50 ℃ instead of r.t.	45
13	2a (2 equiv.)	35
14	5 mA instead of 10 mA	57
15	TMSCF₃ instead of CF₃SO₂Na	Trace
16	No electric current	N.R.
17	n-Bu₄NClO₄ (2 equiv.)	73

Entry	Variation from the standard conditions	Yield^b/%
1	None	77
2	C felt (+) \| C felt(–) Instead of C felt (+) \| Fe (–)	Trace
3	C felt (+) \| Ni felt(–) Instead of C felt (+) \| Fe (–)	62
4	n-Bu₄NPF₆instead of n-Bu₄NClO₄	74
5	n-Bu₄NBF₄instead of n-Bu₄NClO₄	71
6	Without electrolyte	61
7	DCE instead of MeCN	Trace
8	DMF instead of MeCN	Trace
9	AcOH instead of MeCN	52
10	Without H₂O	60
11	H₂O (20 equiv.)	75
12	50 ℃ instead of r.t.	45
13	2a (2 equiv.)	35
14	5 mA instead of 10 mA	57
15	TMSCF₃ instead of CF₃SO₂Na	Trace
16	No electric current	N.R.
17	n-Bu₄NClO₄ (2 equiv.)	73