CNN-Type Binuclear Cu(I) Complexes Catalyzed Direct Carboxylation via the Fixation of CO2 at Room Temperature

doi:10.6023/cjoc202112034

Abstract

A type of CNN-type binuclear Cu(Ⅰ) complexes was used in the direct carboxylation of the terminal alkynes under room temperature and atmospheric CO₂ with a low catalyst loading. A broad range of the terminal alkynes were tolerated, leading to the desired propiolic acids in 83%~97% yields. The method was successfully applied to continuous carboxylation and esterification of hetero arenes. The control experimental results and literature suggest that Cs₂CO₃ promotes the removal of terminal alkyne hydrogen atoms, and Cu(Ⅰ) complexes play an important role in the activation of terminal alkyne by the interaction between Cu(I) center and alkynyl group.

Key words: carbon dioxide, terminal alkyne, copper catalysis, carboxylation, C—H activation

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Fei Chen, Sheng Tao, Ning Liu, Bin Dai. CNN-Type Binuclear Cu(I) Complexes Catalyzed Direct Carboxylation via the Fixation of CO₂ at Room Temperature[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2471-2480.

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Fig. & Tab. 8

References 28

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Entry	Catalyst (mol%)	Base (equiv.)	Time/h	Solvent	Yield/%
1	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMF	92
2	C2 (1.0)	Cs₂CO₃ (1.2)	24	DMF	60
3	C3 (1.0)	Cs₂CO₃ (1.2)	24	DMF	70
4	C4 (1.0)	Cs₂CO₃ (1.2)	24	DMF	50
5	C1 (0.75)	Cs₂CO₃ (1.2)	24	DMF	73
6	C1 (0.50)	Cs₂CO₃ (1.2)	24	DMF	55
7	C1 (0.25)	Cs₂CO₃ (1.2)	24	DMF	36
8	C1 (1.0)	K₂CO₃ (1.2)	24	DMF	8
9	C1 (1.0)	Na₂CO₃ (1.2)	24	DMF	0
10	C1 (1.0)	DBU (1.2)	24	DMF	16
11	C1 (1.0)	Et₃N (1.2)	24	DMF	3
12	C1 (1.0)	K₃PO₄ (1.2)	24	DMF	5
13	C1 (1.0)	NaOH (1.2)	24	DMF	0
14	C1 (1.0)	Na^tOBu (1.2)	24	DMF	4
15	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMA	57
16	C1 (1.0)	Cs₂CO₃ (1.2)	24	THF	14
17	C1 (1.0)	Cs₂CO₃ (1.2)	24	MeCN	23
18	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMSO	60
19	C1 (1.0)	Cs₂CO₃ (1.2)	12	DMF	48
20	C1 (1.0)	Cs₂CO₃ (1.2)	18	DMF	72
21	C1 (1.0)	Cs₂CO₃ (1.2)	30	DMF	94
22	C1 (1.0)	Cs₂CO₃ (1.0)	24	DMF	62
23	C1 (1.0)	Cs₂CO₃ (2.0)	24	DMF	98
24	C1 (1.0)	None	24	DMF	0
25	None	Cs₂CO₃ (1.2)	24	DMF	Trace
26^b	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMF	0

Entry	Catalyst (mol%)	Base (equiv.)	Time/h	Solvent	Yield/%
1	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMF	92
2	C2 (1.0)	Cs₂CO₃ (1.2)	24	DMF	60
3	C3 (1.0)	Cs₂CO₃ (1.2)	24	DMF	70
4	C4 (1.0)	Cs₂CO₃ (1.2)	24	DMF	50
5	C1 (0.75)	Cs₂CO₃ (1.2)	24	DMF	73
6	C1 (0.50)	Cs₂CO₃ (1.2)	24	DMF	55
7	C1 (0.25)	Cs₂CO₃ (1.2)	24	DMF	36
8	C1 (1.0)	K₂CO₃ (1.2)	24	DMF	8
9	C1 (1.0)	Na₂CO₃ (1.2)	24	DMF	0
10	C1 (1.0)	DBU (1.2)	24	DMF	16
11	C1 (1.0)	Et₃N (1.2)	24	DMF	3
12	C1 (1.0)	K₃PO₄ (1.2)	24	DMF	5
13	C1 (1.0)	NaOH (1.2)	24	DMF	0
14	C1 (1.0)	Na^tOBu (1.2)	24	DMF	4
15	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMA	57
16	C1 (1.0)	Cs₂CO₃ (1.2)	24	THF	14
17	C1 (1.0)	Cs₂CO₃ (1.2)	24	MeCN	23
18	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMSO	60
19	C1 (1.0)	Cs₂CO₃ (1.2)	12	DMF	48
20	C1 (1.0)	Cs₂CO₃ (1.2)	18	DMF	72
21	C1 (1.0)	Cs₂CO₃ (1.2)	30	DMF	94
22	C1 (1.0)	Cs₂CO₃ (1.0)	24	DMF	62
23	C1 (1.0)	Cs₂CO₃ (2.0)	24	DMF	98
24	C1 (1.0)	None	24	DMF	0
25	None	Cs₂CO₃ (1.2)	24	DMF	Trace
26^b	C1 (1.0)	Cs₂CO₃ (1.2)	24	DMF	0

CNN型双核Cu(I)配合物室温催化固定CO₂的直接羧基化反应

CNN-Type Binuclear Cu(I) Complexes Catalyzed Direct Carboxylation via the Fixation of CO₂ at Room Temperature

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Entry	Catalyst (mol%)	Base	Solvent	Time/h	T/℃	Yield/%
1	C1 (1.5)	Cs₂CO₃	DMF	18	60	55
2	C2 (1.5)	Cs₂CO₃	DMF	18	60	50
3	C3 (1.5)	Cs₂CO₃	DMF	18	60	49
4	C4 (1.5)	Cs₂CO₃	DMF	18	60	41
5	C1 (3.0)	Cs₂CO₃	DMF	18	60	93
6	C1 (4.5)	Cs₂CO₃	DMF	18	60	91
7	C1 (3.0)	Cs₂CO₃	DMF	12	60	79
8	C1 (3.0)	Cs₂CO₃	DMF	24	60	92
9	C1 (3.0)	K^tOBu	DMF	18	60	72
10	C1 (3.0)	Li^tOBu	DMF	18	60	92
11	C1 (3.0)	Cs₂CO₃	DMF	18	50	64
12	C1 (3.0)	Cs₂CO₃	DMF	18	70	93
13	C1 (3.0)	Cs₂CO₃	DMA	18	60	48
14	C1 (3.0)	Cs₂CO₃	DMSO	18	60	54
15	C1 (3.0)	Cs₂CO₃	THF	18	60	0
16	C1 (3.0)	Cs₂CO₃	CH₃CN	18	60	Trace
17	C1 (3.0)	None	DMF	18	60	0
18	None	Cs₂CO₃	DMF	18	60	0
19^b	C1 (3.0)	Cs₂CO₃	DMF	18	60	0

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Entry	t_1/h	t₂/h	Isolated yield/%
1	4	4	10
2	8	4	9
3	12	4	14
4	4	8	46
5^b			29

Entry	t_1/h	t₂/h	Isolated yield/%
1	4	4	10
2	8	4	9
3	12	4	14
4	4	8	46
5^b			29

CNN型双核Cu(I)配合物室温催化固定CO2的直接羧基化反应