Electrochemical Selenylation of N-Unprotected Anilines for Consturcing 4-(Organylselanyl)anilines

doi:10.6023/cjoc202109044

Abstract

A transition-metal-free and chemical oxidant-free method was developed for the uniform synthesis of 4-arylselanylanilines and 4-alkylselanylanilines through electrolytic selenylation of N-unprotected anilines with diorganyl diselenides under mild conditions in an undivided cell. The present approach had good functional group compatibility, which made it to be a green and practical method to synthesize 4-(organylselanyl)anilines.

Key words: N-unprotected anilines, diorganyl diselenides, electrochemical synthesis, mild conditions, green chemistry

Cite this article

Wenyi Li, Yinheng Tang, Wentao Ouyang, Yuhan Lu, Jinyang Chen, Weimin He. Electrochemical Selenylation of N-Unprotected Anilines for Consturcing 4-(Organylselanyl)anilines[J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4766-4772.

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Entry	Variation from the standard reaction conditions	Yield/%
1	None	95
2	C (+)\|Pt (–) instead of Pt (+)\|Pt (–)	80
3	RVC (+)\|Pt (–) instead of Pt (+)\|Pt (–)	63
4	C (+)\|C (–) instead of Pt (+)\|Pt (–)	63
5	RVC (+)\|RVC (–) instead of Pt (+)\|Pt (–)	34
6	Pt (+)\|Ni foam (–) instead of Pt (+)\|Pt (–)	81
7	ⁿBu₄NBF₄ instead of KI	Trace
8	ⁿBu₄NBr instead of KI	Trace
9	Et₄NClO₄ instead of KI	Trace
10	LiBF₄ instead of KI	Trace
11	ⁿBu₄NI instead of KI	61
12	I₂ (10 mol) instead of KI	70
13	DMF as the solvent	77
14	DMA as the solvent	49
15	DCM as the solvent	16
16	THF as the solvent	9
17	10 mol of KI, 12 h	46
18	30 mol of KI, 6 h	95
19	4 mA instead of 6 mA, 12 h	40
20	12 mA instead of 6 mA, 6 h	89
21	No electric current	N.D.
22	N₂atmosphere instead of air atmosphere	95

Entry	Variation from the standard reaction conditions	Yield/%
1	None	95
2	C (+)\|Pt (–) instead of Pt (+)\|Pt (–)	80
3	RVC (+)\|Pt (–) instead of Pt (+)\|Pt (–)	63
4	C (+)\|C (–) instead of Pt (+)\|Pt (–)	63
5	RVC (+)\|RVC (–) instead of Pt (+)\|Pt (–)	34
6	Pt (+)\|Ni foam (–) instead of Pt (+)\|Pt (–)	81
7	ⁿBu₄NBF₄ instead of KI	Trace
8	ⁿBu₄NBr instead of KI	Trace
9	Et₄NClO₄ instead of KI	Trace
10	LiBF₄ instead of KI	Trace
11	ⁿBu₄NI instead of KI	61
12	I₂ (10 mol) instead of KI	70
13	DMF as the solvent	77
14	DMA as the solvent	49
15	DCM as the solvent	16
16	THF as the solvent	9
17	10 mol of KI, 12 h	46
18	30 mol of KI, 6 h	95
19	4 mA instead of 6 mA, 12 h	40
20	12 mA instead of 6 mA, 6 h	89
21	No electric current	N.D.
22	N₂atmosphere instead of air atmosphere	95

N-无保护苯胺电化学硒醚化反应构建4-(烃基硒代)苯胺