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2024 , Vol. 44 >Issue 10: 3233 - 3240

DOI: https://doi.org/10.6023/cjoc202405049

研究论文

硼促进Co催化使用CO2和H2实现仲芳香胺N-甲基化

  • 石亲 ,
  • 李臻 ,
  • 何林 ,
  • 李玉东 ,
  • 李跃辉
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  • a 中国科学院兰州化学物理研究所 低碳催化与二氧化碳利用国家重点实验室(筹) 羰基合成与选择氧化国家重点实验室 兰州 730000
    b 中国科学院大学 北京 100049
    c 上海交通大学 国家电投智慧能源创新学院 上海 200240

收稿日期: 2024-05-31

  修回日期: 2024-07-16

  网络出版日期: 2024-08-19

基金资助

国家自然科学基金(22022204); 国家自然科学基金(22102197); 江苏省国家自然基金(BK20211096); 江苏省国家自然基金(BK20211093)

收起

Boron-Promoted Co-Catalyzed N-Methylation of Secondary Aromatic Amines with CO2 and H2

  • Qin Shi ,
  • Zhen Li ,
  • Lin He ,
  • Yudong Li ,
  • Yuehui Li
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  • a State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization; State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
    b University of Chinese Academy of Sciences, Beijing 100049
    c College of Smart Energy, Shanghai Jiao Tong University, Shanghai 200240
*E-mail: ;
;

Received date: 2024-05-31

  Revised date: 2024-07-16

  Online published: 2024-08-19

Supported by

National Natural Science Foundation of China(22022204); National Natural Science Foundation of China(22102197); National Science Foundation of Jiangsu Province(BK20211096); National Science Foundation of Jiangsu Province(BK20211093)

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摘要

以CO2/H2为新型甲基化试剂, 对于发展绿色甲基化方法, 建立高效CO2利用新体系具有重要意义. 本工作基于硼活化甲酸根钴中间体策略, 以爪型三膦配体Triphos原位与Co形成催化剂, 实现了温和条件下的N—H甲基化反应. 该体系适用于芳香二级胺类底物, 并表现出优秀的化学选择性和官能团兼容性, 在60~80 ℃反应条件下, 对25个底物反应获得了38%~96%的收率. 基于对照实验结果推测, Lewis酸通过B—O相互作用活化甲酸钴物种, 接受胺分子的亲核进攻生成物种B, 之后脱水生成反应的关键中间体C.

关键词： 二氧化碳/氢气; N-甲基化反应; 钴催化

本文引用格式

石亲 , 李臻 , 何林 , 李玉东 , 李跃辉 . 硼促进Co催化使用CO2和H2实现仲芳香胺N-甲基化[J]. 有机化学, 2024 , 44(10) : 3233 -3240 . DOI: 10.6023/cjoc202405049

Abstract

Development of catalytic methods using CO2/H2 as methylating reagent for selective methylation of amines is highly attractive. Herein, the methylation of N—H bond via boron promoted activation of Co-formate intermediates is reported. This catalytic system showed excellent functional group tolerance with high catalytic activity, and a series of methylated products were acquired in moderate to excellent yields under mild conditions (e.g. 80 ℃ or 60 ℃). It was inferred that imine complex C was the crucial intermediate formed via dehydration of species B, providing efficient C—N coupling for the selective N-methylation of secondary aromatic amines with CO2/H2.

Key words： CO2/H2; N-methylation; cobalt catalysis

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