非负载纳米多孔钯催化喹啉及其衍生物的化学选择性氢化反应:H<sub>2</sub>分子异裂

引用本文: 卢烨, Yoshinori Yamamoto, Abdulrahman I. Almansour, Natarajan Arumugam, Raju Suresh Kumar, 包明. 非负载纳米多孔钯催化喹啉及其衍生物的化学选择性氢化反应:H₂分子异裂[J]. 催化学报, 2018, 39(11): 1746-1752. doi: 10.1016/S1872-2067(18)63151-1 shu

Citation: Ye Lu, Yoshinori Yamamoto, Abdulrahman I. Almansour, Natarajan Arumugam, Raju Suresh Kumar, Ming Bao. Unsupported nanoporous palladium-catalyzed chemoselective hydrogenation of quinolines:Heterolytic cleavage of H₂ molecule[J]. Chinese Journal of Catalysis, 2018, 39(11): 1746-1752. doi: 10.1016/S1872-2067(18)63151-1 shu

非负载纳米多孔钯催化喹啉及其衍生物的化学选择性氢化反应:H₂分子异裂

a 大连理工大学精细化工国家重点实验室, 辽宁大连 116023, 中国;
b 东北大学理学研究科化学系, 仙台980-8578, 日本;
c 立命馆大学科学技术研究所, 草津, 志贺525-8577, 日本;
d 沙特阿拉伯国王大学科学学院化学系, 2455 信箱, 利雅得 11451, 沙特阿拉伯
基金项目:
国家自然科学基金（21573032，21773021）；中央高校基本科研业务费专项资金（DUT17ZD212）；沙特国王大学国际合作项目（ISPP#0048）.

摘要: 纳米多孔金属是近十年发展起来的一类具有三维通孔结构的新型功能材料，其由纳米尺度的细孔和韧带构成，具有极大的比表面积；它还是一种无毒无载体的宏观材料，并且易制备、易回收和重复利用，因此作为高效的非均相催化剂已逐渐引起人们的重视.
1，2，3，4-四氢喹啉是许多医药、农药、染料和天然产物的重要骨架.通过喹啉及其衍生物的选择性加氢反应制备1，2，3，4-四氢喹啉，具有原子利用率高和原料易得等优点.在过去，已经开发了许多类型的均相和非均相催化体系，并成功地用于催化喹啉及其衍生物的选择性加氢反应.尽管非均相催化体系具有诸多优点，但仍存在H₂压力（10-50 atm）和反应温度（60-150℃）相对较高的缺点.因此，开发更加温和条件下的喹啉及其衍生物的选择性加氢反应具有重要意义.此外，在喹啉及其衍生物的加氢反应过程中，H₂分子在非均相催化剂表面的裂解模式，即均裂还是异裂尚不清楚.因此，本文采用新型非均相催化剂纳米多孔钯，研究了喹啉及其衍生物的选择性加氢反应，在相对较低的H₂压力（2-5 atm）和温度（室温-50℃）下实现了目标反应，高收率、高选择性地得到1，2，3，4-四氢喹啉化合物.
在最佳反应条件下，对底物的适用范围进行了考察.结果表明，各种含喹啉结构单元的化合物均能顺利发生反应，产物收率在62%-95%.而且该反应对甲基、甲氧基、羟基、酯基、醛基、酰胺基、卤素（F，Cl和Br）等官能团具有较好的兼容性.苯环上取代基的电子效应对反应有一定的影响，吸电子基有利于目标反应的进行.
反应完成后，纳米多孔钯催化剂很容易回收，且循环使用多次后，仍未见催化活性降低.扫描电镜和透射电镜结果发现，循环使用后的纳米多孔钯催化剂结构没有发生明显改变，表明其结构稳定.浸出实验结果证明，没有钯原子浸出到反应液中，表明该纳米多孔钯催化反应属于多相催化过程.喹啉的选择性氢化反应被放大到克级的规模时，目标产物的收率仅略有降低，说明该方法具有很好的实用性.通过动力学实验发现，随着反应的进行，反应速率不断加快，表明反应过程中生成的乙胺和1，2，3，4-四氢喹啉同样扮演着路易斯碱性添加剂的角色，促进了反应的进行.通过反应机理研究，揭示了H-H键在纳米多孔钯表面发生了异裂，原位形成的Pd-H物种作为弱亲核试剂，对目标反应的选择性控制起到了至关重要的作用.

关键词:

English

Unsupported nanoporous palladium-catalyzed chemoselective hydrogenation of quinolines:Heterolytic cleavage of H₂ molecule

a State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, Liaoning, China;
b Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan;
c Research Organization of Science and Technology, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan;
d Department of Chemistry, College of Sciences, King Saud University, P. O. Box 2455, Riyadh 11451, Saudi Arabia
Received Date: 26 June 2018
Revised Date: 29 July 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (21573032, 21773021), the Fundamental Research Funds for the Central Universities (DUT17ZD212), and the International Scientific Partnership Program ISPP at King Saud University for funding this research work through ISPP#0048.

Abstract: An efficient and highly chemoselective heterogeneous catalyst system for quinoline hydrogenation was developed using unsupported nanoporous palladium (PdNPore). The PdNPore-catalyzed chemoselective hydrogenation of quinoline proceeded smoothly under mild reaction conditions (low H₂ pressure and temperature) to yield 1,2,3,4-tetrahydroquinolines (py-THQs) in satisfactory to excellent yields. Various synthetically useful functional groups, such as halogen, hydroxyl, formyl, ethoxycarbonyl, and aminocarbonyl groups, remained intact during the quinoline hydrogenation. No palladium was leached from PdNPore during the hydrogenation reaction. Moreover, the catalyst was easily recovered and reused without any loss of catalytic activity. The results of kinetic, deuterium-hydrogen exchange, and deuterium-labeling experiments indicated that the present hydrogenation involves heterolytic H₂ splitting on the surface of the catalyst.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

非负载纳米多孔钯催化喹啉及其衍生物的化学选择性氢化反应:H₂分子异裂

English

Unsupported nanoporous palladium-catalyzed chemoselective hydrogenation of quinolines:Heterolytic cleavage of H₂ molecule

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

非负载纳米多孔钯催化喹啉及其衍生物的化学选择性氢化反应:H2分子异裂

English

Unsupported nanoporous palladium-catalyzed chemoselective hydrogenation of quinolines:Heterolytic cleavage of H2 molecule

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

非负载纳米多孔钯催化喹啉及其衍生物的化学选择性氢化反应:H₂分子异裂

Unsupported nanoporous palladium-catalyzed chemoselective hydrogenation of quinolines:Heterolytic cleavage of H₂ molecule

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs