Electrochemical Oxidative Cross-Dehydrogenative Coupling of Five-Membered Aromatic Heterocycles with NH4SCN

doi:10.6023/cjoc202207009

Abstract

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

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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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References 12

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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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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

Electrochemical Oxidative Cross-Dehydrogenative Coupling of Five-Membered Aromatic Heterocycles with NH₄SCN

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