CuI催化C—C键偶联反应构建2-羰基-1,4-二酮

doi:10.6023/cjoc202506032

摘要/Abstract

过渡金属催化的C—C偶联反应是有机合成中构建碳-碳键的核心策略, 其发展不仅推动了药物、材料和天然产物的合成, 还不断在机理创新和催化剂设计上取得突破. 在此基础上, 报道了在铜催化条件下酮类之间发生的自由基反应, 利用该反应可以实现2-羰基-1,4-二酮化合物的合成. 该方法对多种结构类型的酮(包括取代基多样的脂肪酮、芳香酮和各种不限于丙酮的简单酮)均表现出优异的适用性, 用途广泛, 易于实施, 催化剂毒性低, 成本效益高, 且产物易于分离纯化.

关键词: 过渡金属催化, C—C偶联, 自由基反应, 2-羰基-1,4-二酮

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

引用此文

刘颖杰, 闵来生, 杨锐蓉, 宋冬雪, 彭瑞, 梁德强. CuI催化C—C键偶联反应构建2-羰基-1,4-二酮[J]. 有机化学, 2026, 46(2): 603-611.

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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参考文献 23

[1]	(a) Kumar S.; Jyoti J.; Gupta D. SynOpen 2023, 7, 580. doi: 10.1055/s-0040-1720096
	(b) Perez Sestelo J.; Sarandeses L. A. Molecules 2020, 25, 4500. doi: 10.3390/molecules25194500
	(c) Song F.; Wang B.; Shi Z. J. Acc. Chem. Res. 2023, 56, 2867. doi: 10.1021/acs.accounts.3c00230
	(d) Wickham L. M.; Giri R. Acc. Chem. Res. 2021, 54, 3415. doi: 10.1021/acs.accounts.1c00329
	(e) Duan A.; Xiao F.; Lan Y.; Wang C.; Liu. L.; Zhang Z. Chem. Soc. Rev. 2022, 51, 9986. doi: 10.1039/D2CS00371F
[2]	(a) Yorimitsu H.; Kotora M.; Patil, N T. Chem. Rec. 2021, 21, 3335. doi: 10.1002/tcr.v21.12 pmid: 37163671
	(b) Docherty J. H.; Lister T. M.; Mcarthur G.; Findlay J. R.; Kerr W. J.; Andersson H. M.; Donohoe T. J. Chem. Rev. 2023, 123, 7692. doi: 10.1021/acs.chemrev.2c00888 pmid: 37163671
	(c) Bag D, Mahajan S, Sawant, S D. Adv. Synth. Catal. 2020, 362, 3948. doi: 10.1002/adsc.v362.19 pmid: 37163671
[3]	(a) Gramage-Doria R.; Bruneau C. Synthesis 2023, 55, 3470. doi: 10.1055/a-2134-0307
	(b) Lee H. E.; Kim D.; You A.; Kim S.; Lee P. H. Catalysts 2020, 10, 861. doi: 10.3390/catal10080861
	(c) Butcher T. W.; Amberg W. M.; Hartwig J. F. Angew. Chem. Int. Ed. 2022, 61, e202112251.
[4]	(a) Wu T.; Tang W. Chem.-Eur. J. 2021, 27, 3944. doi: 10.1002/chem.v27.12
	(b) Pati B. V.; Puthalath N. N.; Banjare S. K.; Nanda T.; Ravikumar P. C. Org. Biomol. Chem. 2023, 21, 2842. doi: 10.1039/D3OB00238A
	(c) Lu H.; Yu T. Y.; Xu P. F.; Wei H. Chem. Rev. 2020, 121, 365. doi: 10.1021/acs.chemrev.0c00153
	(d) Bi X.; Zhang Q.; Gu Z. Chin. J. Chem. 2021, 39, 1397. doi: 10.1002/cjoc.v39.5
[5]	(a) Deepthi A.; Babu B. P.; Balachandran A. L. Org. Prep. Proced. Int. 2019, 51, 409. doi: 10.1080/00304948.2019.1633228
	(b) Kaur N, Grewal P, Poonia, K. Synth. Commun. 2021, 51, 2423.
[6]	(a) Pelkey, E T. In Heterocyclic Chemistry, Vol. 11, Eds.Eds.: Gribble, G. W.; Gilchrist, T. L., Elsevier, Oxford, 1999, p. 102.
	(b) Kornfeld E. C.; Jones R. G. J. Org. Chem. 1954, 19, 1671. doi: 10.1021/jo01375a017
[7]	(a) Iqbal S.; Rasheed H.; Awan R. J.; Awan R. J.; Mukhtar A.; Moloney M. G. Curr. Org. Chem. 2020, 24, 1196. doi: 10.2174/1385272824999200528125651
	(b) Ferreira V. F.;de Souza, M. C. B. V.; Cunha, A. C.; Pereira, L. O. R.; Ferreira, M. L. G. Org. Prep. Proced. Int. 2001, 33, 411. doi: 10.1080/00304940109356613
[8]	(a) Vartanyan R. S. Pharm. Chem. J. 1983, 17, 329. doi: 10.1007/BF00765637
	(b) Nagai Y.; Uno H.; Umemoto S. Chem. Pharm. Bull. 1977, 25, 1911. doi: 10.1248/cpb.25.1911
[9]	Zhou W.; Voituriez A. Org. Lett. 2020, 23, 247. doi: 10.1021/acs.orglett.0c04023
[10]	Chen X. Y.; Enders D. Angew. Chem., Int. Ed. 2019, 58, 6488. doi: 10.1002/anie.v58.20
[11]	Lemmerer M.; Schupp M.; Kaiser D.; Maulide N. Nat. Synth. 2022, 1, 923. doi: 10.1038/s44160-022-00179-1
[12]	(a) Liu C.; Deng Y.; Wang J.; Yang Y.; Tang S.; Lei A. Angew. Chem., Int. Ed. 2011, 50,7337.
	(b) Fujisawa T.; Igeta K.; Odake S.; Morita Y.; Yasuda J.; Morikawa T. Bioorg. Med. Chem. 2002, 10, 2569. doi: 10.1016/S0968-0896(02)00109-8
[13]	(a) Heravi M. M.; Zadsirjan V.; Kafshdarzadeh K.; Masoumi B. Asian J. Org. Chem. 2020, 9, 1999. doi: 10.1002/ajoc.202000378
	(b) Stetter H. Angew. Chem., Int. Ed. Engl. 1976, 15, 639. doi: 10.1002/anie.v15:11
[14]	(a) Jang H. Y.; Hong J. B.; MacMillan D. W. C. J. Am. Chem. Soc. 2007, 129, 7004. doi: 10.1021/ja0719428
	(b) Clift M. D.; Taylor C. N.; Thomson R. J. Org. Lett. 2007, 9, 4667. doi: 10.1021/ol702306z
[15]	(a) Parida B. B.; Das P. P.; Niocel M.; Cha J. K. Org. Lett. 2013, 15, 1780. doi: 10.1021/ol400666x
	(b) Shen Z. L.; Goh K. K. K.; Cheong H. L.; Wong C. H. A.; Lai Y. C.; Yang Y. S.; Loh T. P. J. Am. Chem. Soc. 2010, 132, 15852. doi: 10.1021/ja106925f
	(c) Custar D. W.; Le H.; Morken J. P. Org. Lett. 2010, 12, 3760. doi: 10.1021/ol1013476
	(d)Xue S.; Li, L. Z.; Liu, Y. K.; Guo, Q. X. J. Org. Chem. 2006, 71, 215. doi: 10.1021/jo051950b
	(e) Stepherson J. R.; Fronczek F. R.; Kartika R. Chem. Commun. 2016, 52, 2300. doi: 10.1039/C5CC09763K
[16]	Kaldre D.; Klose I.; Maulide N. Science 2018, 361, 664. doi: 10.1126/science.aat5883
[17]	Kobatake T.; Yoshida S.; Yorimitsu H.; Oshima K. Angew. Chem., Int. Ed. 2010, 49, 2340. doi: 10.1002/anie.v49:13
[18]	Huang S.; Kötzner L.; De C. K.; List B. J. Am. Chem. Soc. 2015, 137, 3446. doi: 10.1021/ja511200j
[19]	Jadhav A. M.; Gawade S. A.; Vasu D.; Dateer R. B.; Liu R. S. Chem.-Eur. J. 2014, 20, 1813. doi: 10.1002/chem.v20.7
[20]	Dong Y.; Li R.; Zhou J.; Sun Z. Org. Lett. 2021, 23, 6387. doi: 10.1021/acs.orglett.1c02208 pmid: 34339208
[21]	Amaya T.; Maegawa Y.; Masuda T, Osawa T.; Shimizu Y.; Oe Y.; Kobayashi T. J. Am. Chem. Soc. 2015, 137, 10072. doi: 10.1021/jacs.5b05058 pmid: 26244707
[22]	Lv Y.; Pu W.; Niu J.; Zhao Q.; Wang Z.; Li X. Tetrahedron Lett. 2018, 59, 1497. doi: 10.1016/j.tetlet.2018.03.011
[23]	Li Y.; Yang R.; Zhao X.; Yang Y.; Wang Y.; Li Y. Synth. Commun. 2019, 49, 735. doi: 10.1080/00397911.2019.1574350

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