KI-Catalyzed Selective C(5)-Sulfenylation and C(5),C(7)-Disulfenylation of Unprotected 8-Aminoquinolines and the Indole C(2),C(3)-Disulfenylation

doi:10.6023/cjoc202206029

Abstract

The aromatic C—H sulfenylation reactions of unprotected 8-aminoquinolines have been realized by employing KI as the only catalyst at 2.5 mol% loading without using any transition metal reagent. Interestingly, the selective C(5)-sulfenylation and C(5),C(7)-disulfenylation have been successfully achieved by simply controlling the reaction time. Reaction time of 12 h in p-xylene enables the C(5)-sulfenylation. On the other hand, prolonging the reaction time to 24 h and switching the reaction medium to toluene lead to the selective C(5),C(7)-double sulfenylation. Moreover, the double sulfenylation has been extended to the indole substrate for the selective synthesis of 2,3-disulfenyl indoles.

Key words: C—H functionalization, free radical, 8-aminoquinoline, selectivity, sulfenylation

Cite this article

Haozhi Wu, Tian Luo, Jianwen Jiang, Jieping Wan. KI-Catalyzed Selective C(5)-Sulfenylation and C(5),C(7)-Disulfenylation of Unprotected 8-Aminoquinolines and the Indole C(2),C(3)-Disulfenylation[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3721-3729.

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Entry	Catalyst	Solvent	Temp./℃	Yield^b/%
Entry	Catalyst	Solvent	Temp./℃	3a	4a
1	KI	p-Xylene	120	36	0
2	TBAI	p-Xylene	120	36	0
3	I₂	p-Xylene	120	27	0
4	NIS	p-Xylene	120	33	0
5	NaI	p-Xylene	120	26	Trace
6^c	KI	p-Xylene	120	32	0
7^d	KI	p-Xylene	120	34	0
8	KI	p-Xylene	110	26	0
9	KI	p-Xylene	130	35	0
10	KI	Toluene	120	30	43
11	KI	DMF	120	25	0
12	KI	DMSO	120	0	0
13^e	KI	p-Xylene	120	32	0
14^f	KI	p-Xylene	120	60	Trace
15^g	KI	p-Xylene	120	52	0
16^h	KI	Toluene	120	Trace	57
17^h	KI	Toluene	110	21	43
18^h^,ⁱ	KI	Toluene	120	Trace	74
19^h^,^j	KI	Toluene	120	Trace	84
20^k	KI	Toluene	120	0	0
21	—	Toluene	120	0	0

Entry	Catalyst	Solvent	Temp./℃	Yield^b/%
Entry	Catalyst	Solvent	Temp./℃	3a	4a
1	KI	p-Xylene	120	36	0
2	TBAI	p-Xylene	120	36	0
3	I₂	p-Xylene	120	27	0
4	NIS	p-Xylene	120	33	0
5	NaI	p-Xylene	120	26	Trace
6^c	KI	p-Xylene	120	32	0
7^d	KI	p-Xylene	120	34	0
8	KI	p-Xylene	110	26	0
9	KI	p-Xylene	130	35	0
10	KI	Toluene	120	30	43
11	KI	DMF	120	25	0
12	KI	DMSO	120	0	0
13^e	KI	p-Xylene	120	32	0
14^f	KI	p-Xylene	120	60	Trace
15^g	KI	p-Xylene	120	52	0
16^h	KI	Toluene	120	Trace	57
17^h	KI	Toluene	110	21	43
18^h^,ⁱ	KI	Toluene	120	Trace	74
19^h^,^j	KI	Toluene	120	Trace	84
20^k	KI	Toluene	120	0	0
21	—	Toluene	120	0	0

碘化钾催化无保护8-氨基喹啉的选择性C(5)-芳基硫醚化和C(5),C(7)-双芳基硫醚化及吲哚C(2),C(3)-双芳基硫醚化反应