氮掺杂碳材料负载Pd纳米结构催化剂催化硝基芳烃与苄醇借氢还原偶联制备亚胺

doi:10.6023/cjoc202007046

摘要/Abstract

亚胺化合物作为一类重要的有机合成中间体, 在医药、染料以及精细化学品制备方面具有重要的应用价值. 使用竹笋为生物质原料制备一种氮掺杂碳材料负载的Pd纳米结构催化剂, 以醇为氢源和反应物, 通过借氢还原策略实现硝基芳烃原位还原并偶联反应高效制备亚胺化合物. 该催化剂相对于其他商业化的催化剂和载体具有明显的性能优势, 催化体系具有良好的底物适用性和官能团兼容性. 此外, 该催化剂具有良好的催化稳定性, 能够循环使用多次并保持催化活性不变.

关键词: 氮掺杂碳材料, Pd纳米颗粒, 硝基芳烃, 苄醇, 借氢, 亚胺化合物

Imines as a versatile organic synthetic intermediates have important applications in pharmaceuticals, dyes, and fine chemicals. In this work, heterogeneous Pd nanoparticles (Pd@N,O-carbon) on N doped carbon materials were developed using bamboo shoot as raw materials for highly efficient reductive coupling of nitroarenes with alcohols to selectively synthesize imines via the borrowing hydrogen strategy. The catalyst has obvious advantages in catalytic performance compared with other commercial catalysts or supports. Meanwhile, a broad set of complex imines were successfully synthesized in good yields with various functional groups tolerance for both nitroarenes and alcohols. This heterogeneous catalyst can also be recycled at several times without significant loss in activity and selectivity.

Key words: N doped carbon materials, Pd nanoparticles, nitroarenes, benzyl alcohols, borrowing hydrogen, imines

引用此文

车佳宁, 宋涛, 高先池, 杨勇. 氮掺杂碳材料负载Pd纳米结构催化剂催化硝基芳烃与苄醇借氢还原偶联制备亚胺[J]. 有机化学, 2021, 41(1): 276-283.

Jianing Che, Tao Song, Xianchi Gao, Yong Yang. Borrowing Hydrogen Reductive Coupling of Nitroarenes with Benzyl Alcohols to Imines Catalyzed by Pd Nanoparticles on N Doped Carbon Materials[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 276-283.

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图/表 9

Scheme 1. 借氢还原策略制备胺类化合物

. Synthesis of imines or amines via the borrowing hydrogen strategy

Figure 1. Pd@N,O-carbon制备示意图

. Schematic illustration of the typical procedure for the synthesis of Pd@N,O-carbon

Entry	Solvent	Base (equiv.)	Conv. ^b /%	3a ^b /%	4a ^b /%
1	Toluene	t-BuOK (2.5)	59	59	60
2	Toluene	t-BuOK (3.0)	100	>99	0
3 ^c	Toluene	t-BuOK (3.0)	100	>99	0
4 ^c	Toluene	t-BuOK (4.0)	100	0	>99
5	Toluene	KHMDS (3.0)	100	40	60
6	Toluene	NaOH (3.0)	32	24	8
7	Toluene	Na₂CO₃(3.0)	0	0	0
8 ^d	Toluene	t-BuOK (3.0)	100	>99	0
9 ^e	Toluene	t-BuOK (3.0)	100	>99	0
10 ^f 11 ^g	Toluene Toluene	t-BuOK (3.0) t-BuOK (3.0)	63 40	63 40	0 0
12 ^d	2-Methyl-THF	t-BuOK (3.0)	86	9	1
13 ^d	Dioxane	t-BuOK (3.0)	38	17	0
13 ^d	CH₃CN	t-BuOK (3.0)	100	0	0
14 ^d	n-Hexane	t-BuOK (3.0)	51	23	0

表1. 反应条件优化 a

Table 1. Optimization of the reaction conditions

Entry	[Pd]	Con./%	3a/%	4a/%
1	Pd/AC	66	6	60
2	Pd/Al₂O₃	21	18	3
3	Pd/TiO₂	100	69	31
4	Pd/ZrO₂	81	72	9
5	Pd/CeO₂	68	55	13
6	Pd/MgO	30	28	2
7	Pd/g-C₃N₄	89	73	16

表2. 催化剂对照实验 a

Table 2. Comparison of Pd catalysts prepared using different supports

Scheme 4. 对照实验

. Control experiments

图2. 催化剂循环实验

Figure 2. Recycling performance of catalyst

表3. 硝基苯和醇偶联合成亚胺 a

Table 3. Synthesis of imines from various alcohols and nitroarenes

图式5. 硝基芳烃和醇借氢还原偶联制备亚胺反应可能的机理

Scheme 5. Proposed mechanism for reductive coupling of nitroarenes and alcohols via the borrowing hydrogen strategy

图3. Pd@N,O-carbon催化剂移除影响实验

Figure 3. Effect of removal of the Pd@N,O-carbon catalyst (○) after removal of Pd@N,O-carbon, and (●) without removal of Pd@N,O-carbon.

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