电化学促进的五元芳香杂环与硫氰酸铵氧化交叉脱氢偶联反应

doi:10.6023/cjoc202207009

摘要/Abstract

报道了一种无化学氧化剂、无外加电解质条件下电化学促进的五元芳香杂环化合物(吡唑、咪唑、呋喃和噻吩)与硫氰酸铵发生氧化交叉脱氢偶联反应合成硫氰基五元芳香杂环化合物的方法. 反应中, 硫氰酸铵发挥着电解质和硫氰化试剂的双重作用, 简化了反应体系.

关键词: 五元芳香杂环化合物, 电化学合成, 脱氢偶联反应, 双作用, 绿色化学

A practical method for the synthesis of various thiocyanated 5-membered aromatic heterocycles through electrochemical cross-coupling of heterocycles (pyrazoles, pyrroles, furans and thiophenes) with NH₄SCN under chemical oxidant- and exogenous electrolyte-free conditions was developed. NH₄SCN played dual roles of a supporting electrolyte and a thiocyanated reagent, and thus simplify the reaction system.

Key words: five-membered heterocycles, electrochemical synthesis, cross-dehydrogenative coupling reaction, dual roles, green chemistry

引用此文

李红霞, 陈棚, 伍智林, 陆雨函, 彭俊梅, 陈锦杨, 何卫民. 电化学促进的五元芳香杂环与硫氰酸铵氧化交叉脱氢偶联反应[J]. 有机化学, 2022, 42(10): 3398-3404.

Hongxia Li, Peng Chen, Zhilin Wu, Yuhan Lu, Junmei Peng, Jingyang Chen, Weimin He. Electrochemical Oxidative Cross-Dehydrogenative Coupling of Five-Membered Aromatic Heterocycles with NH₄SCN[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3398-3404.

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Entry	Condition	Yield^b/%
1	No change	91 (88)^c
2	Pt(+)\|Pt(–) instead of Pt(+)\|Al foam (–)	72
3	Pt(+)\|C(–) instead of Pt(+)\|Al foam (–)	82
4	Pt(+)\|Fe(–) instead of Pt(+)\|Al foam (–)	84
5	Pt(+)\|Cu(–) instead of Pt(+)\|Al foam (–)	16
6	C (+)\|Pt(–) instead of Pt(+)\|Al foam (–)	89
7	C(+)\|C(–) instead of Pt(+)\|Al foam (–)	38
8	C(+)\|Al foam (–) instead of C(+)\|Pt(–)	75
9	RVC(+)\|Al foam (–) instead of Pt(+)\|Al foam (–)	85
10	KSCN instead of NH₄SCN	67
11	NaSCN instead of NH₄SCN	82
12	DMF instead of MeCN	16
13	DMSO instead of MeCN	Trace
14	EtOH instead of MeCN	Trace
15	Acetone instead of MeCN	Trace
16	15 mA, 15 h	87
17	Without electric current	N.R.

Entry	Condition	Yield^b/%
1	No change	91 (88)^c
2	Pt(+)\|Pt(–) instead of Pt(+)\|Al foam (–)	72
3	Pt(+)\|C(–) instead of Pt(+)\|Al foam (–)	82
4	Pt(+)\|Fe(–) instead of Pt(+)\|Al foam (–)	84
5	Pt(+)\|Cu(–) instead of Pt(+)\|Al foam (–)	16
6	C (+)\|Pt(–) instead of Pt(+)\|Al foam (–)	89
7	C(+)\|C(–) instead of Pt(+)\|Al foam (–)	38
8	C(+)\|Al foam (–) instead of C(+)\|Pt(–)	75
9	RVC(+)\|Al foam (–) instead of Pt(+)\|Al foam (–)	85
10	KSCN instead of NH₄SCN	67
11	NaSCN instead of NH₄SCN	82
12	DMF instead of MeCN	16
13	DMSO instead of MeCN	Trace
14	EtOH instead of MeCN	Trace
15	Acetone instead of MeCN	Trace
16	15 mA, 15 h	87
17	Without electric current	N.R.

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