华东师范大学学报(自然科学版) ›› 2023, Vol. 2023 ›› Issue (1): 12-20.doi: 10.3969/j.issn.1000-5641.2023.01.002

• 原子经济性反应 • 上一篇    下一篇

双齿含氧配体修饰Co2(CO)8催化环氧丙 (乙) 烷羰化酰胺化反应制备β-羟基酰胺

郭琳1, 时广辉1, 陈晓超1, 刘晔1,2,*()   

  1. 1. 华东师范大学 化学与分子工程学院 上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
    2. 崇明生态研究院, 上海 202162
  • 收稿日期:2022-06-21 接受日期:2022-09-16 出版日期:2023-01-25 发布日期:2023-01-07
  • 通讯作者: 刘晔 E-mail:yliu@chem.ecnu.edu.cn
  • 基金资助:
    国家自然科学基金 (22172052, 21972045)

Aminocarbonylation of propylene (ethylene) epoxide over Co2(CO)8 catalyst modified by bidental O-containing ligand for synthesis of β-hydroxy amides

Lin GUO1, Guanghui SHI1, Xiaochao CHEN1, Ye LIU1,2,*()   

  1. 1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
    2. Institute of Eco-Chongming, Shanghai 202162, China
  • Received:2022-06-21 Accepted:2022-09-16 Online:2023-01-25 Published:2023-01-07
  • Contact: Ye LIU E-mail:yliu@chem.ecnu.edu.cn

摘要:

首次报道了以芳香胺为氨源, 通过双齿含氧配体L2修饰Co2(CO)8催化环氧化合物的羰化酰胺化反应, 一步合成β-羟基酰胺化合物的方法. 在温和的条件下 (60℃、CO 3.0 MPa、6 h), 以L2修饰的Co2(CO)8作为催化剂, 能够实现环氧丙烷和苯胺的羰化酰胺化反应, 得到收率为64%的3-羟基-N-苯基丁酰胺目标产物; 该催化剂体系具有较好的稳定性和一定的底物普适性. 其中, 双齿含氧配体L2通过双氧水氧化双齿膦配体Xantphos (9,9-二甲基-4,5-双二苯基膦-氧杂蒽) 制得.

关键词: 环氧丙烷, 环氧乙烷, 羰化酰胺化反应, Co2(CO)8, β-羟基酰胺

Abstract:

This work reports a one-step protocol for the synthesis of β-hydroxyamides via amino-carbonylation of epoxides using aromatic amines as the ammonia source instead of silylamine. The reaction was catalyzed by Co2(CO)8 modified with bidentate O-containing ligand L2, which was prepared by the oxidation of Xantphos [9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene] by H2O2 as a diphosphine-dioxide. Under mild conditions (60 °C, CO 3.0 MPa, 6 h), L2-modified Co2(CO)8 efficiently catalyzed the amino-carbonylation of propylene oxide with aniline to generate 3-hydroxy-N-phenylbutanamide with the yield of 64%. The developed catalytic system exhibited fair stability and general substrate scope.

Key words: propylene oxide, ethylene oxide, aminocarbonylation, Co2(CO)8, β-hydroxy amides

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