镍/可见光协同催化的溴代芳烃与醇的C—O键偶联反应

doi:10.6023/cjoc202506009

摘要/Abstract

研究了镍/可见光协同催化的溴代芳烃/杂芳烃与醇的C—O键偶联反应. 在456 nm蓝光的照射下, 以有机光敏剂2,4,5,6-四(9-咔唑基)间苯二腈(4CzIPN)或者2,4,5,6-四(二苯胺基)间苯二腈(4DPAIPN)为光催化剂, 以乙二醇二甲醚溴化镍(NiBr₂•DME)、配体和碱为协同催化体系, 高效地实现了烷基芳基醚类化合物的合成. 该反应的可能历程为: Ni(0)中间体先与溴代芳烃发生氧化加成, 再与醇进行配体交换; 生成的Ni(II)中间体被激发态光催化剂氧化为Ni(III)中间体, 继而发生还原消除反应. 该反应具有良好的底物适用性, 可以用于苄醇、一级醇与二级醇的转化, 且官能团兼容性较好.

关键词: 镍催化, 可见光, C—O键偶联, 烷基芳基醚

A nickel/visible light dual-catalyzed C—O bond coupling reaction between aryl/heteroaryl bromides and alcohols has been developed. Alkyl aryl ethers were efficiently synthesized by using organic photoredox-catalyst 2,4,5,6-tetra(9H-

carbazol-9-yl)isophthalonitrile (4CzIPN) or 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DPAIPN) in the presence of nickel(II) bromide 1,2-dimethoxyethane (NiBr₂•DME), a ligand, and a base under 456 nm blue LED irradiation at room temperature. The reaction likely involves the oxidative addition of Ni(0) intermediate to aryl bromide, ligand exchange with the alcohol, oxidization of the resulting Ni(II) intermediate by the excited photoredox catalyst to form Ni(III) intermediate, and subsequent reductive elimination. This method exhibits broad substrate scope of alcohols, including benzyl alcohols, primary alcohols, and secondary alcohols, and with remarkable functional group tolerance.

Key words: nickel-catalysis, visible light, C—O bond coupling, alkyl aryl ethers

引用此文

高山, 解鑫, 刘元红. 镍/可见光协同催化的溴代芳烃与醇的C—O键偶联反应[J]. 有机化学, 2026, 46(1): 266-278.

Shan Gao, Xin Xie, Yuanhong Liu. Nickel/Visible Light Dual-Catalyzed C—O Bond Coupling Reactions of Aryl Bromides with Alcohols[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 266-278.

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Entry	Photoredox-catalyst	Ni catalyst (mol%)	Ligand (mol%)	Base
1	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	^tBuOLi	59
2	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	Cs₂CO₃	5
3	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	MeOLi	65
4	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	88
5	4CzIPN	NiBr₂•DME (10)	L1 (10)	K₃PO₄	2
6	4CzIPN	NiBr₂•DME (10)	L2 (10)	K₃PO₄	68
7	4CzIPN	NiBr₂•DME (10)	L3 (10)	K₃PO₄	81
8	4CzIPN	NiCl₂•6H₂O (10)	dtbbpy (10)	K₃PO₄	79
9	[Ir(dFCF₃ppy)₂dtbbpy]PF₆	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	78
10	[Ir(dtbbpy)(ppy)₂]PF₆	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	50
11	4CzIPN	NiBr₂•DME (5)	dtbbpy (6)	K₃PO₄	88
12	4CzIPN	Ni(cod)₂(5)	dtbbpy (6)	K₃PO₄	84
13	—	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	1
14	4CzIPN	—	dtbbpy (10)	K₃PO₄	0
15	4CzIPN	NiBr₂•DME (10)	—	K₃PO₄	0
16	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	—	0
17^b	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	0
18^c	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	0

Entry	Photoredox-catalyst	Ni catalyst (mol%)	Ligand (mol%)	Base
1	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	^tBuOLi	59
2	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	Cs₂CO₃	5
3	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	MeOLi	65
4	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	88
5	4CzIPN	NiBr₂•DME (10)	L1 (10)	K₃PO₄	2
6	4CzIPN	NiBr₂•DME (10)	L2 (10)	K₃PO₄	68
7	4CzIPN	NiBr₂•DME (10)	L3 (10)	K₃PO₄	81
8	4CzIPN	NiCl₂•6H₂O (10)	dtbbpy (10)	K₃PO₄	79
9	[Ir(dFCF₃ppy)₂dtbbpy]PF₆	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	78
10	[Ir(dtbbpy)(ppy)₂]PF₆	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	50
11	4CzIPN	NiBr₂•DME (5)	dtbbpy (6)	K₃PO₄	88
12	4CzIPN	Ni(cod)₂(5)	dtbbpy (6)	K₃PO₄	84
13	—	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	1
14	4CzIPN	—	dtbbpy (10)	K₃PO₄	0
15	4CzIPN	NiBr₂•DME (10)	—	K₃PO₄	0
16	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	—	0
17^b	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	0
18^c	4CzIPN	NiBr₂•DME (10)	dtbbpy (10)	K₃PO₄	0