镍催化多氟芳烃与烷基卤化物的还原烷基化反应

doi:10.6023/cjoc202502007

有机化学 ›› 2025, Vol. 45 ›› Issue (6): 2121-2127.DOI: 10.6023/cjoc202502007 上一篇下一篇

研究论文

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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摘要/Abstract

多氟芳烃是医学和材料化学中一类重要的化合物, 但制备烷基化多氟芳烃仍然具有挑战性. 在此, 报道了在温和条件下镍催化的多氟芳烃与烷基卤化物的还原烷基化反应. 多氟芳烃(含3~6个F的结构)可与多种类型烷基卤化物(如伯、仲、叔烷基碘化物)顺利反应. 通过Ni催化和(Bpin)₂/K₂CO₃作为终端还原剂的结合, 实现了C(sp²)—C(sp³)键的高效生成.

关键词: 镍催化, 多氟芳烃, 烷基卤代物, 还原偶联

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

引用此文

谢沈彤, 李文静, 刘钰, 陆熹, 师仁义. 镍催化多氟芳烃与烷基卤化物的还原烷基化反应[J]. 有机化学, 2025, 45(6): 2121-2127.

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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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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