基于简单高效钯纳米粒子催化Suzuki偶联反应的研究

doi:10.6023/cjoc201904069

摘要/Abstract

一种简单、高效的钯纳米粒子催化体系被用于Suzuki偶联反应中.该催化体系对含各种官能团的卤代芳烃和芳基硼酸都表现出了非常高的催化活性.当用对硝基溴苯作底物时，在催化剂用量低至0.001 mol%时转化数能达到90000，这也证实了该催化体系有比较好的稳定性和较长的寿命.

关键词: 卤代芳烃, 芳基硼酸, 钯纳米粒子, Suzuki偶联

A simple and highly efficient palladium nanoparticles catalytic system was applied in Suzuki coupling reaction. This system could catalyze a variety of aryl halide and arylboronic acid substrates with a wide range of functional groups. A high turnover number of 90000 was obtained with the catalyst loading as low as 0.001 mol%. This catalyst system exhibited good stability and longevity.

Key words: aryl hailde, arylboronic acid, palladium nanoparticle, Suzuki coupling

引用此文

李恒超, 赵玲, 刘燕, 张霞, 李王兵, 敬林海, 黄锦, 汪伟. 基于简单高效钯纳米粒子催化Suzuki偶联反应的研究[J]. 有机化学, 2019, 39(11): 3207-3214.

Li Hengchao, Zhao Ling, Liu Yan, Zhang Xia, Li Wangbing, Jing Linhai, Huang Jin, Wang Wei. An Efficient Palladium Nanoparticles Catalytic System for Suzuki Coupling Reactions[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3207-3214.

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图/表 6

图式 1. 钯/四齿膦配体催化卤代芳烃的Suzuki偶联反应

Scheme 1. Pd/tetraphosphine-catalyzed Suzuki coupling reaction of aryl halides

图式 2. 钯纳米粒子催化体系在有机合成中的应用

Scheme 2. Application of palladium nanoparticles catalytic system in organic synthesis


Entry	Base	Solvent	TBAB/mmol	Time/h	Yield^b/%
1	Et₃N	DMA	0.375	8	0
2	NaOAc	DMA	0.375	8	0
3	NaHCO₃	DMA	0.375	8	10
4	Na₂CO₃	DMA	0.375	8	17
5	K₂CO₃	DMA	0.375	8	100
6	K₃PO₄	DMA	0.375	8	88
7	NaOH	DMA	0.375	8	19
8	K₂CO₃	DMA	0.375	2	96
9	K₂CO₃	DMF	0.375	2	100
10	K₂CO₃	1, 4-Dioxane	0.375	2	58
11	K₂CO₃	n-Butanol	0.375	2	26
12	K₂CO₃	Toluene	0.375	2	63
13	K₂CO₃	DMF	0.125	1	94
14	K₂CO₃	DMF	0.25	1	85
15	K₂CO₃	DMF	0.375	1	79
16	K₂CO₃	DMF	0.5	1	84

表 1. 优化反应条件a

Table 1. Optimization of reaction conditions

图 1. 反应动力学曲线和汞中毒实验

Figure 1. Conversion vs. time plot for Suzuki reactionReaction conditions: 1a (0.5 mmol), 2a (1.0 mmol), [Pd(C3H5)Cl]2 (0.0005 mmol), K2CO3 (1.0 mmol), DMF (1.0 mL), TBAB (0.125 mmol), under argon, 100 ℃). (■) Control experiment; (○) Hg(0) (0.5 mmol) poisoning experiment

表 2. 对硝基氯苯与芳基硼酸的Suzuki偶联反应a

Table 2. Suzuki coupling of 4-nitrochlorobenzene with arylboronic acids

表 3. 卤代芳烃与苯硼酸的Suzuki偶联反应a

Table 3. Suzuki coupling of aryl halides with phenylboronic acid

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