有机化学 ›› 2022, Vol. 42 ›› Issue (4): 1216-1223.DOI: 10.6023/cjoc202110018 上一篇    下一篇

研究论文

荧光染料和镍协同催化的脱羧羰基化反应

余卫国a,*(), 王灵娜b, 俞晓聪b, 罗书平b,*()   

  1. a 浙江药科职业大学 药物化学研究所 浙江宁波 315100
    b 浙江工业大学 绿色化学合成技术国家重点实验室培育基地 杭州 310014
  • 收稿日期:2021-10-13 修回日期:2021-11-24 发布日期:2021-12-02
  • 通讯作者: 余卫国, 罗书平
  • 基金资助:
    浙江省基础公益基金(LGG21H300001); 浙江省教育厅科研基金(Y201432790)

Fluorescent Dye/Nickel Synergistic Catalytic Decarboxylative Carbonylation Reaction

Weiguo Yua(), Lingna Wangb, Xiaocong Yub, Shuping Luob()   

  1. a Institute of Medicinal Chemistry, Zhejiang Pharmaceutical Colloge, Ningbo, Zhejiang 315100
    b State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014
  • Received:2021-10-13 Revised:2021-11-24 Published:2021-12-02
  • Contact: Weiguo Yu, Shuping Luo
  • Supported by:
    Basic Public Welfare Fund of Zhejiang Province(LGG21H300001); Scientific Research Fund of Zhejiang Provincial Education Department(Y201432790)

在荧光染料与镍协同催化下, 以N-苯甲酰基琥珀酰亚胺类化合物为羰基化试剂, 实现了α-氨基酸的脱羧羰基化反应. 该反应以较好的收率(最高可达78%)合成了16种含α-氨基酮的衍生物, 光转化效率最高可达3.25×10–1 mmol/ (kW•h). 此外, 提出了该光催化反应的可能机理: α-氨基羧酸在可见光催化下生成α-氨基烷基自由基, 并进入镍催化循环中, 经过氧化加成和还原消除过程后生成α-氨基酮类化合物. 该反应可以在温和条件下合成不同种类的α-氨基酮类化合物, 显示了良好的底物适应性, 可能在含有α-氨基酮的药物分子合成及肽的化学修饰等方面具有很广泛的应用价值.

关键词: 光催化, 镍催化, 单电子转移, 脱羧偶联反应

The decarboxylative carbonylation of α-amino acids was carried out with N-benzoyl succinimide as the carbonylation reagent under the synergistic catalysis of fluorescent dye/nickel catalysts. In this reaction, 16 kinds of α-amino ketone-containing derivatives were synthesized with good yields (up to 78%), and the light conversion efficiency was up to 3.25×10–1 mmol/(kW•h). In addition, the possible mechanism of the photocatalytic reaction was proposed: α-amino carboxylic acid was catalyzed by visible light to form α-amino alkyl radicals, which entered the nickel catalytic cycle and produced α-amino ketone target compound via oxidation addition and reduction elimination process. The reactions could generate a variety of α-amino ketones with broad substrate scope under mild conditions and might have widespread use in synthesis of α-amino ketone-containing drug molecules and peptide modifications.

Key words: photocatalysis, nickel catalysis, single electron transfer, decarboxylative coupling reaction