Ni-Catalyzed Reductive Alkylation of Polyfluoroarenes with Alkyl Halides

doi:10.6023/cjoc202502007

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (6): 2121-2127.DOI: 10.6023/cjoc202502007 Previous Articles Next Articles

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镍催化多氟芳烃与烷基卤化物的还原烷基化反应

谢沈彤^a^,^†, 李文静^a^,^†, 刘钰^a, 陆熹^b, 师仁义^a^,^*()

^a 西安交通大学化学工程与技术学院西安 710049
^b 中国科学技术大学应用化学系合肥 230026

收稿日期:2025-02-06 修回日期:2025-03-20 发布日期:2025-04-16
通讯作者: 师仁义
作者简介:
^†共同第一作者.
基金资助:
西安交通大学“青年人才支持计划”和陕西省自然科学基金(2023-JC-QN-0102)

Ni-Catalyzed Reductive Alkylation of Polyfluoroarenes with Alkyl Halides

Shentong Xie^a^,^†, Wenjing Li^a^,^†, Yu Liu^a, Xi Lu^b, Renyi Shi^a^,^*()

^a School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an 710049
^b Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026

Received:2025-02-06 Revised:2025-03-20 Published:2025-04-16
Contact: Renyi Shi
About author:
^†The authors contributed equally to this work.
Supported by:
“Young Talent Support Plan” of Xi'an Jiaotong University and the Natural Science Foundation of Shaanxi Province(2023-JC-QN-0102)

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Abstract

Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry. It is still a challenge to synthesize alkylated polyfluoroarenes. Herein, a Ni-catalyzed reductive alkylation of polyfluoroarenes with alkyl halides under mild conditions is reported. Polyfluoroarenes (3~6 F) can reacted smoothly with a diverse range of alkyl halides, such as primary, secondary, and tertiary alkyl iodides. The efficient formation of C(sp²)—C(sp³) can be achieved through the combination of Ni catalysis and (Bpin)₂/K₂CO₃ as terminal reductant.

Key words: nickel catalysis, polyfluoroarenes, alkyl halides, reductive cross-coupling

Cite this article

Shentong Xie, Wenjing Li, Yu Liu, Xi Lu, Renyi Shi. Ni-Catalyzed Reductive Alkylation of Polyfluoroarenes with Alkyl Halides[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2121-2127.

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Fig. & Tab. 4

References 16

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Entry	Catalyst (mol%)	L (mol%)	Reductant	Base (equiv.)	Solvent	Yield^b/%
1	NiBr₂•dme (10)	bpy (15)	Zn	—	DMA	7
2	NiBr₂•dme (10)	bpy (15)	Mn	—	DMA	4
3	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	DMA	24
4	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	THF	18
5	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	CH₂Cl₂	Trace
6	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	1,4-Dioxane	36
7	NiBr₂•dme (10)	bpy (15)	B₂pin₂	Na₂CO₃ (2)	1,4-Dioxane	0
8	NiBr₂•dme (10)	bpy (15)	B₂pin₂	Cs₂CO₃ (2)	1,4-Dioxane	28
9	NiBr₂•dme (10)	bpy (12)	B₂pin₂	CsF (2)	1,4-Dioxane	0
10	NiBr₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃(2)	1,4-Dioxane	42
11	NiBr₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃(2.5)	1,4-Dioxane	45
12	NiBr₂•dme (5)	py (12)	B₂pin₂	K₂CO₃(2.5)	1,4-Dioxane	11
13	NiBr₂•dme (5)	phen (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	14
14	NiCl₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	47
15	NiCl₂ (5)	bpy (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	21
16^d	NiCl₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	69
17^e	NiCl₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃(2.5)	1,4-Dioxane	75 (72^c)

Entry	Catalyst (mol%)	L (mol%)	Reductant	Base (equiv.)	Solvent	Yield^b/%
1	NiBr₂•dme (10)	bpy (15)	Zn	—	DMA	7
2	NiBr₂•dme (10)	bpy (15)	Mn	—	DMA	4
3	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	DMA	24
4	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	THF	18
5	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	CH₂Cl₂	Trace
6	NiBr₂•dme (10)	bpy (15)	B₂pin₂	K₂CO₃ (2)	1,4-Dioxane	36
7	NiBr₂•dme (10)	bpy (15)	B₂pin₂	Na₂CO₃ (2)	1,4-Dioxane	0
8	NiBr₂•dme (10)	bpy (15)	B₂pin₂	Cs₂CO₃ (2)	1,4-Dioxane	28
9	NiBr₂•dme (10)	bpy (12)	B₂pin₂	CsF (2)	1,4-Dioxane	0
10	NiBr₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃(2)	1,4-Dioxane	42
11	NiBr₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃(2.5)	1,4-Dioxane	45
12	NiBr₂•dme (5)	py (12)	B₂pin₂	K₂CO₃(2.5)	1,4-Dioxane	11
13	NiBr₂•dme (5)	phen (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	14
14	NiCl₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	47
15	NiCl₂ (5)	bpy (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	21
16^d	NiCl₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃ (2.5)	1,4-Dioxane	69
17^e	NiCl₂•dme (5)	bpy (6)	B₂pin₂	K₂CO₃(2.5)	1,4-Dioxane	75 (72^c)

镍催化多氟芳烃与烷基卤化物的还原烷基化反应

Ni-Catalyzed Reductive Alkylation of Polyfluoroarenes with Alkyl Halides

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