Acta Chim. Sinica ›› 2016, Vol. 74 ›› Issue (6): 472-487.DOI: 10.6023/A16030153 Previous Articles     Next Articles



邱頔a, 邱孟龙a, 马戎a, 张艳b, 王剑波b   

  1. a 天津师范大学化学学院 天津市功能分子结构与性能重点实验室 无机-有机杂化功能材料化学教育部重点实验室 天津 300387;
    b 北京大学化学与分子工程学院 生物有机与分子工程教育部重点实验室 北京分子科学国家实验室 北京100871
  • 投稿日期:2016-03-29 发布日期:2016-04-26
  • 通讯作者: 邱頔
  • 基金资助:

    项目受天津师范大学引进人才人事专项资助(No. 5RL138).

Nitrogen Group Retaining Reaction in the Transformation of Diazo Compounds

Qiu Dia, Qiu Menglonga, Ma Ronga, Zhang Yanb, Wang Jianbob   

  1. a Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid Functional Materials Chemistry of Ministry of Education, College of Chemistry, Tianjin Normal University, Tianjin 300387;
    b Beijing National Laboratory of Molecular Sciences BNLMS and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871
  • Received:2016-03-29 Published:2016-04-26
  • Supported by:

    Project supported by the scientific research funding of Tianjin Normal University (No. 5RL138).

Diazo compounds represent a type of very important synthetic intermediates, which demonstrate wide applications in organic synthesis, continuous-in-flow technology, polymer synthesis, medicinal chemistry, chemical biology, material science and many other fields. On the other hand, diazo intermediates can be easily prepared from commercial available substrates through facile transformations, such as base-promoted decomposition of N-tosylhydrazones, diazo-transfer reaction, diazotization of alkyl amines, oxidation of hydrazones, decomposition of N-nitroso compounds. Traditional transformations of diazo compounds include nucleophilic addition/substitution by using diazo compounds as the nucleophiles, ylide type reactions, dimerization or olefination, Wolff rearrangement, transition-metal-carbene or carbenoid mediated X—H insertion reactions, catalytic cyclopropanations or cyclopropenations, and the recently developed transition-metal-catalyzed carbenoid cross-coupling reactions. In addition to these classic reactions, the diazo compounds also undergo nitrogen group retaining reactions, in which the diazo moiety is incorporated into the nitrogen-containing moiety in the target molecules. This strategy has provided an efficient and selective synthetic approach towards nitrogen atom containing functional molecules, especially for the synthesis of various N-heterocyclic compounds. Among them, the enantioselective C—N bond forming reaction as well as the asymmetric N-heterocyclic scaffold construction has important synthetic value and remains great challenge to the organic chemists. Thus, nitrogen component retaining reactions of diazo compounds has opened up a superior avenue in organic synthesis. Considering about the significant importance and the great growth in the past decade of this area, this review article will focus on the nitrogen group retaining reaction of diazo compounds. According to the reaction mechanism of these transformations, this review will be divided into the following parts: diazo compounds as nucleophiles, diazo compounds as 1,3-dipoles in cycloaddition reaction, diazo compounds as electrophiles, intramolecular reactions of vinyldiazo compounds, reduction reaction, and miscellaneous transformation. We hope that this review will corroborate the practical use of this research area as a convenient and valuable synthetic strategy.

Key words: diazo compound, organic synthesis, N-heterocycle, cycloaddition