Copper-Catalyzed Allylic C(sp3)—H Sulfonylation of Cyclic Olefins

doi:10.6023/cjoc202211028

Abstract

A highly efficient copper-catalyzed direct sulfonylation of allylic C(sp³)—H bond was developed using simple cyclic olefins and sodium sulfite as starting materials. A series of allylic sulfone derivatives were synthesized in moderate to good yields under mild conditions. The mechanism study shows that the reaction might involve radical intermediates.

Key words: copper-catalyzed, radicals, allylic C(sp³)—H, sulfonation reaction, allylic sulfone

Cite this article

Chunyang Liu, Yan Li, Qian Zhang. Copper-Catalyzed Allylic C(sp³)—H Sulfonylation of Cyclic Olefins[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1091-1101.

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Fig. & Tab. 6

References 16

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Entry	Cu cat.	Ligand	Solvent	T/℃	Yield/%
1	CuBr	L1	DCM	30	48
2	CuBr	L2	DCM	30	42
3	CuBr	L3	DCM	30	62
4	CuBr	L4	DCM	30	75
5	CuBr	L5	DCM	30	37
6	CuBr	L6	DCM	30	51
7	CuCl	L4	DCM	30	69
8	CuOAc	L4	DCM	30	43
9	CuI	L4	DCM	30	73
10	Cu(CH₃CN)₄PF₆	L4	DCM	30	78
11	Cu(CH₃CN)₄PF₆	L4	DCE	30	82
12	Cu(CH₃CN)₄PF₆	L4	THF	30	0
13	Cu(CH₃CN)₄PF₆	L4	PhCF₃	30	0
14	Cu(CH₃CN)₄PF₆	L4	CH₃CN	30	52
15	Cu(CH₃CN)₄PF₆	L4	DCE	10	87
16	Cu(CH₃CN)₄PF₆	L4	DCE	50	73
17	None	L4	DCE	10	0
18^b	Cu(CH₃CN)₄PF₆	L4	DCE	10	0
19	Cu(CH₃CN)₄PF₆	None	DCE	10	18
20^c	Cu(CH₃CN)₄PF₆	L4	DCE	10	45

Entry	Cu cat.	Ligand	Solvent	T/℃	Yield/%
1	CuBr	L1	DCM	30	48
2	CuBr	L2	DCM	30	42
3	CuBr	L3	DCM	30	62
4	CuBr	L4	DCM	30	75
5	CuBr	L5	DCM	30	37
6	CuBr	L6	DCM	30	51
7	CuCl	L4	DCM	30	69
8	CuOAc	L4	DCM	30	43
9	CuI	L4	DCM	30	73
10	Cu(CH₃CN)₄PF₆	L4	DCM	30	78
11	Cu(CH₃CN)₄PF₆	L4	DCE	30	82
12	Cu(CH₃CN)₄PF₆	L4	THF	30	0
13	Cu(CH₃CN)₄PF₆	L4	PhCF₃	30	0
14	Cu(CH₃CN)₄PF₆	L4	CH₃CN	30	52
15	Cu(CH₃CN)₄PF₆	L4	DCE	10	87
16	Cu(CH₃CN)₄PF₆	L4	DCE	50	73
17	None	L4	DCE	10	0
18^b	Cu(CH₃CN)₄PF₆	L4	DCE	10	0
19	Cu(CH₃CN)₄PF₆	None	DCE	10	18
20^c	Cu(CH₃CN)₄PF₆	L4	DCE	10	45

铜催化环状烯烃烯丙位C(sp³)—H磺酰化反应研究

Copper-Catalyzed Allylic C(sp³)—H Sulfonylation of Cyclic Olefins

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铜催化环状烯烃烯丙位C(sp3)—H磺酰化反应研究