CuI-Catalyzed C—C Bond Coupling Reaction for the Construction of 2-Carbonyl-1,4-diketones

doi:10.6023/cjoc202506032

Abstract

Transition metal-catalyzed C—C coupling reactions are a core strategy for the construction of carbon-carbon bonds in organic synthesis. Their development has not only promoted the synthesis of drugs, materials, and natural products, but also promoted the development of new synthetic methods, and has also made breakthroughs in mechanism innovation and catalyst design. On this basis, a copper-catalyzed radical reaction between ketones is reported, enabling the synthesis of 2-carbonyl-1,4- diones. The method exhibits excellent applicability to multiple structural types of ketones, including aliphatic ketones with diverse substituents, aromatic ketones, and various simple ketones not limited to acetone, with wide applications, easy implementation, low catalyst toxicity, and low cost, cost-effective, and the product is easy to separate and purify.

Key words: transition metal catalysis, C—C coupling, radical reaction, 2-carbonyl-1,4-dione

Cite this article

Yingjie Liu, Laisheng Min, Ruirong Yang, Dongxue Song, Rui Peng, Deqiang Liang. CuI-Catalyzed C—C Bond Coupling Reaction for the Construction of 2-Carbonyl-1,4-diketones[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 603-611.

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Entry	Catalyst (mol%)	Initiator (equiv.)	Solvent	T/℃	t/h	Yield ^b/%
1	TsOH•H₂O (10)	TBHP (3)	Acetone	120	6	18
2	CuI (10)	TBHP (3)	Acetone	120	6	30
3	AgNO₃ (10)	TBHP (3)	Acetone	120	6	0
4	CoCl₂•6H₂O (10)	TBHP (3)	Acetone	120	6	0
5	CuI (10)	DTBP (3)	Acetone	120	6	18
6	CuI (10)	DCP (3)	Acetone	120	6	62
7	CuI (10)	BPO (3)	Acetone	120	6	43
8	CuI (10)	TBPB (3)	Acetone	120	6	53
9	CuI (10)	K₂S₂O₈ (3)	Acetone	120	6	11
10	CuI (10)	DCP (3)	DCM＋10 equiv. acetone	120	6	0
11	CuI (10)	DCP (3)	DCE＋10 equiv. acetone	120	6	0
12	CuI (10)	DCP (3)	THF＋10 equiv. acetone	120	6	0
13	CuI (10)	DCP (3)	DMF＋10 equiv. acetone	120	6	0
14	CuI (10)	DCP (3)	Methanol＋10 equiv. acetone	120	6	Trace
15	CuI (10)	DCP (3)	V(acetone)∶V(THF)=1∶2	120	6	0
16	CuI (10)	DCP (3)	V(acetone)∶V(MeNO₂)=1∶2	120	6	Trace
17	CuI (10)	DCP (3)	V(acetone)∶V(DCM)=1∶2	120	6	32
18	CuI (10)	DCP (3)	V(acetone)∶V(toluene)=1∶2	120	6	41
19	CuI (10)	DCP (3)	V(acetone)∶V(DMF)=1∶2	120	6	0
20	CuI (10)	DCP (3)	V(acetone)∶V(methanol)=1∶2	120	6	Trace
21	CuI (10)	DCP (3)	V(acetone)∶V(chlorobenzene)=1∶2	120	6	41
22	CuI (10)	DCP (3)	Acetone	140	6	78
23	CuI (10)	DCP (3)	Acetone	80	6	Trace
24	CuBr (10)	DCP (3)	Acetone	140	6	35
25	CuCl (10)	DCP (3)	Acetone	140	6	47
26	Cu₂O (10)	DCP (3)	Acetone	140	6	52
27	CuCl₂•2H₂O (10)	DCP (3)	Acetone	140	6	49
28	Cu(OAc)₂ (10)	DCP (3)	Acetone	140	6	18
29	CuSO₄•5H₂O (10)	DCP (3)	Acetone	140	6	56
30	Cu(NO₃)₂•3H₂O (10)	DCP (3)	Acetone	140	6	38
31	TBAI (10)	DCP (3)	Acetone	140	6	45
32	CuI (20)	DCP (3)	Acetone	140	6	53
33	CuI (5)	DCP (3)	Acetone	140	6	68
34	CuI (10)	DCP (5)	Acetone	140	6	45
35	CuI (10)	DCP (4)	Acetone	140	6	55
36	CuI (10)	DCP (2)	Acetone	140	6	67
37	CuI (10)	DCP (1.2)	Acetone	140	6	36

Entry	Catalyst (mol%)	Initiator (equiv.)	Solvent	T/℃	t/h	Yield ^b/%
1	TsOH•H₂O (10)	TBHP (3)	Acetone	120	6	18
2	CuI (10)	TBHP (3)	Acetone	120	6	30
3	AgNO₃ (10)	TBHP (3)	Acetone	120	6	0
4	CoCl₂•6H₂O (10)	TBHP (3)	Acetone	120	6	0
5	CuI (10)	DTBP (3)	Acetone	120	6	18
6	CuI (10)	DCP (3)	Acetone	120	6	62
7	CuI (10)	BPO (3)	Acetone	120	6	43
8	CuI (10)	TBPB (3)	Acetone	120	6	53
9	CuI (10)	K₂S₂O₈ (3)	Acetone	120	6	11
10	CuI (10)	DCP (3)	DCM＋10 equiv. acetone	120	6	0
11	CuI (10)	DCP (3)	DCE＋10 equiv. acetone	120	6	0
12	CuI (10)	DCP (3)	THF＋10 equiv. acetone	120	6	0
13	CuI (10)	DCP (3)	DMF＋10 equiv. acetone	120	6	0
14	CuI (10)	DCP (3)	Methanol＋10 equiv. acetone	120	6	Trace
15	CuI (10)	DCP (3)	V(acetone)∶V(THF)=1∶2	120	6	0
16	CuI (10)	DCP (3)	V(acetone)∶V(MeNO₂)=1∶2	120	6	Trace
17	CuI (10)	DCP (3)	V(acetone)∶V(DCM)=1∶2	120	6	32
18	CuI (10)	DCP (3)	V(acetone)∶V(toluene)=1∶2	120	6	41
19	CuI (10)	DCP (3)	V(acetone)∶V(DMF)=1∶2	120	6	0
20	CuI (10)	DCP (3)	V(acetone)∶V(methanol)=1∶2	120	6	Trace
21	CuI (10)	DCP (3)	V(acetone)∶V(chlorobenzene)=1∶2	120	6	41
22	CuI (10)	DCP (3)	Acetone	140	6	78
23	CuI (10)	DCP (3)	Acetone	80	6	Trace
24	CuBr (10)	DCP (3)	Acetone	140	6	35
25	CuCl (10)	DCP (3)	Acetone	140	6	47
26	Cu₂O (10)	DCP (3)	Acetone	140	6	52
27	CuCl₂•2H₂O (10)	DCP (3)	Acetone	140	6	49
28	Cu(OAc)₂ (10)	DCP (3)	Acetone	140	6	18
29	CuSO₄•5H₂O (10)	DCP (3)	Acetone	140	6	56
30	Cu(NO₃)₂•3H₂O (10)	DCP (3)	Acetone	140	6	38
31	TBAI (10)	DCP (3)	Acetone	140	6	45
32	CuI (20)	DCP (3)	Acetone	140	6	53
33	CuI (5)	DCP (3)	Acetone	140	6	68
34	CuI (10)	DCP (5)	Acetone	140	6	45
35	CuI (10)	DCP (4)	Acetone	140	6	55
36	CuI (10)	DCP (2)	Acetone	140	6	67
37	CuI (10)	DCP (1.2)	Acetone	140	6	36

CuI催化C—C键偶联反应构建2-羰基-1,4-二酮