有机化学 ›› 2019, Vol. 39 ›› Issue (7): 2042-2047.DOI: 10.6023/cjoc201901012 上一篇    下一篇

研究简报

全氟烷基磺酰氟活化羧酸和1,3-二羰基化合物之间一步O-酰基化反应

严兆华a, 王彦梅a, 金红爱a, 艾城美a, 田伟生b   

  1. a 南昌大学化学学院 南昌 330031;
    b 中国科学院上海有机化学研究所 上海 200032
  • 收稿日期:2019-01-10 修回日期:2019-03-24 出版日期:2019-07-25 发布日期:2019-04-09
  • 通讯作者: 严兆华, 田伟生 E-mail:yanzh@ncu.edu.cn;wstian@sioc.ac.cn
  • 基金资助:

    国家自然科学基金(No.21362022)资助项目.

One-Step Enol Esterification of 1,3-Dicarbonyls with Carboxylic Acids Activated by Perfluoroalkanosulfonyl Fluoride

Yan Zhaohuaa, Wang Yanmeia, Jin Hong'aia, Ai Chengmeia, Tian Weishengb   

  1. a College of Chemistry, Nanchang University, Nanchang 330031;
    b Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2019-01-10 Revised:2019-03-24 Online:2019-07-25 Published:2019-04-09
  • Contact: 10.6023/cjoc201901012 E-mail:yanzh@ncu.edu.cn;wstian@sioc.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21362022).

碱性介质中,羧酸在全氟烷基磺酰氟活化下与1,3-二酮化合物和β-酮酸酯能发生一步O-酰基化反应,以中等到良好的产率生成相应的烯醇酯产物.

关键词: 全氟烷基磺酰氟, 1,3-二羰基化合物, 羧酸, 烯醇酯

O-Acylation of 1,3-dicarbonyl compounds provides enol esters which act as precursors for the synthesis of chiral alcohols, natural products, heterocycles and functional materials. Perfluoroalkanosulfonyl fluoride (RfSO2F) is a class of excellent hydroxyl-activating reagent, and has been extensively developed and used in the formation of C-F, C-O, C-N and C-S bonds in organic synthesis. In this work one-step O-acylation of 1,3-dicarbonyl compounds (1,3-diketones and β-ketonic esters) with carboxylic acids activated by RfSO2F in alkaline media was disclosed, and the corresponding O-acylation products (enol esters) were generated in moderate to good yields. The optimized reaction conditions are as follows:1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) as base, CH2Cl2 as solvent, n-C4F9SO2F as activating reagent, room temperature for 30 min and the molar ratio of n(1,3-dicarbonyls):n(RCOOH):n(RfSO2F):n(DBU) being 1.0:1.0:1.0:4.0. A novel reagent for one-step O-acylation of 1,3-dicarbonyl compounds with carboxylic acids was developed. The application of RfSO2F in organic synthesis was further expanded.

Key words: perfluoroalkanosulfonyl fluoride, 1,3-dicarbonyl compound, carboxylic acids, enol ester