COF固载铜盐催化苯硼酸与咪唑的Chan-Lam偶联反应

doi:10.7503/cjcu20190630

摘要/Abstract

摘要：

制备了一种含有联吡啶位点的共价有机骨架(COF)材料TpBpy, 并通过配体上的联吡啶位点固载铜盐实现了功能化, 得到的Cu@TpBpy具有大量的不饱和铜配位位点和高表面积, 可用作苯硼酸与咪唑的Chan-Lam偶联反应的多相催化剂. 通过优化溶剂、铜源、碱及反应时间等反应条件, 发现使用质子极性溶剂MeOH时的反应产率最高, 而Cu(OAc)₂@TpBpy是效果最佳的催化剂, 可溶性有机碱三乙胺(TEA)的促进效果最好. Cu(OAc)₂@TpBpy在碱TEA的促进下于70 ℃催化咪唑与苯硼酸反应4 h后, 得到目标产物1-苯基咪唑的最大产率为66%. 在最优反应条件下进行了底物拓展, 结果表明, 取代基的位阻效应对催化体系影响显著, 其中对位取代基的4-氯苯硼酸的产率最高(62%).

关键词: 共价有机骨架, 铜基催化剂, Chan-Lam偶联, C—N偶联, 非均相催化

Abstract:

A bipyridine containing covalent organic framework(COF), namely TpBpy, modified with copper ions was prepared. The obtained Cu@TpBpy was used as a heterogeneous catalyst for C—N cross-coupling reaction of arylboronic acid with imidazole. To optimize the reaction conditions, we have screened various parameters such as the catalyst, solvent, base and reaction time. The experimental result showed that using the polar solvent MeOH gives the best yield with the promotion of base TEA, while Cu(OAc)₂@TpBpy is the optimal catalyst. The reaction achieves maximum yield of 66% after 4 h reaction catalyzed by Cu(OAc)₂@TpBpy with TEA in MeOH at 70 ℃. In the optimal reaction conditions, arylboronic acid with different substituents were examined in the coupling reaction with imidazole, among them, 4-chlorophenylboric acid showed the best yield of 62%.

Key words: Covalent organic framework, Copper-based catalyst, Chan-Lam coupling, C—N cross-coupling, Heterogeneous catalysis

中图分类号:

O643.32 ⁺2

TrendMD:

刘恒烁,遇治权,孙志超,王瑶,刘颖雅,王安杰. COF固载铜盐催化苯硼酸与咪唑的Chan-Lam偶联反应. 高等学校化学学报, 2020, 41(5): 1091.

LIU Hengshuo,YU Zhiquan,SUN Zhichao,WANG Yao,LIU Yingya,WANG Anjie. Copper Salt Anchored on a Covalent Organic Framework as Heterogeneous Catalyst for Chan-Lam Coupling Reaction ^†. Chem. J. Chinese Universities, 2020, 41(5): 1091.

图/表 14

Scheme 1 Solvothermal synthetic route of TpBpy

Scheme 2 Schematic reprentation of Cu(OAc)2 anchored on bipyridine sites of TpBpy to obtain Cu(OAc)2@TpBpy to catalyze the coupling reaction of imidazole and phenylboronic acid

Table 1 Corresponding solvents used for different copper sources

Entry	Cu source	Modification solvent
1	CuI	Acetonitrile
2	Cu(NO₃)₂·3H₂O	Ethanol
3	CuCl₂	Ethanol
4	Cu₂Cl₂	DMSO
5	Cu(OAc)₂·H₂O	Ethanol
6	CuSO₄·5H₂O	DMF
7	Cu(CF₃SO₃)₂	Acetonitrile

Fig.1 PXRD pattern(A), FTIR spectrum(B), N2 adsorption-desorption isotherms(C) and TGA curve(D) of TpBpy

Fig.2 FESEM(A) and TEM(B) images of TpBpy

Fig.3 PXRD pattern(A), FTIR spectra(B) and N2 adsorption-desorption isotherms(C) of TpBpy(a) and Cu(OAc)2@TpBpy(b)

Fig.4 XPS spectra of Cu(OAc)2@TpBpy(A) and CuI@TpBpy(B) in Cu2p region

Table 2 Optimization of Chan-Lam coupling reaction conditionsa

Entry	Solvent	Catalyst	Base	GC yield(%)	Isolated yield(%)
1^b	EtOH	—	TEA	—	—
2^c	EtOH	TpBpy	TEA	—	—
3^d	EtOH	CuI@TpBpy	TEA	—	—
4	EtOH	CuI@TpBpy	TEA	22
5	MeOH	CuI@TpBpy	TEA	39	38
6	MeOH	CuCl₂@TpBpy	TEA	23	21
7	MeOH	Cu(NO₃)₂@TpBpy	TEA	19
8	MeOH	Cu(CF₃SO₃)₂@TpBpy	TEA	61
9	MeOH	Cu₂Cl₂@TpBpy	TEA	32
10	MeOH	CuSO₄@TpBpy	TEA	51
11	MeOH	Cu(OAc)₂@TpBpy	TEA	66
12	DMSO	Cu(OAc)₂@TpBpy	TEA	6
13	DMF	Cu(OAc)₂@TpBpy	TEA	Trace
14	1,4-Dioxane	Cu(OAc)₂@TpBpy	TEA	Trace
15	DCM	Cu(OAc)₂@TpBpy	TEA	—
16	1,2-Dichloroethane	Cu(OAc)₂@TpBpy	TEA	—
17	Toluene	Cu(OAc)₂@TpBpy	TEA	Trace
18^e	MeOH	Cu(OAc)₂@TpBpy	—	44
19	MeOH	Cu(OAc)₂@TpBpy	Na₂CO₃	37
20	MeOH	Cu(OAc)₂@TpBpy	K₂CO₃	18
21	MeOH	Cu(OAc)₂@TpBpy	pyridine	45

Fig.5 1H NMR spectrum of 1-phenyl-imidazole

Fig.6 PXRD patterns of Cu(OAc)2@TpBpy before(a) and after(b) reaction under the best reaction conditions

Fig.7 GC yield-time profile for the coupling reaction in methanol with Cu(OAc)2@TpBpy as catalyst Phenylboronic acid(0.82 mmol, 100 mg), imidazole(0.98 mmol), TEA(0.98 mmol), Cu(OAc)2@TpBpy(10%, molar fraction), MeOH 5 mL, 70 ℃.

Table 3 Homogeneous reaction of imidazole and phenylboronic acida

Entry	Solvent	Catalyst	Yield^b(%)
1	MeOH	CuI	62
2	MeOH	Cu(NO₃)₂·3H₂O	71
3	MeOH	CuCl₂	68
4	MeOH	Cu₂Cl₂	68
5	MeOH	Cu(OAc)₂·H₂O	81

Table 4 Cu@TpBpy catalyzed N-arylation of imidazole with arylboronic acidsa

Entry	Boronic acid	Amine	Product	Yield ^b(%)
1				44
2				62
3				54
4				53
5				Trace
6				Trace
7				59
8				41

Scheme 3 Plausible catalytic cycle for the coupling reaction of imidazole and phenylboronic acid

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