Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (1): 196-202.DOI: 10.6023/cjoc201608008 Previous Articles     Next Articles

NOTE

全氟烷基磺酰氟应用于1,3-二羰基化合物和苄醇衍生物之间一步C-或O-苄基化反应

严兆华a, 金红爱a, 余信权a, 王汪阳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:2016-08-11 修回日期:2016-09-07 出版日期:2017-01-25 发布日期:2016-09-12
  • 通讯作者: 严兆华, 田伟生 E-mail:yanzh@ncu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21362022)资助项目.

One-Step C- or O-Benzylation of 1,3-Dicarbonyls with Benzyl Alcohols Promoted by Perfluoroalkanosulfonyl Fluoride

Yan Zhaohuaa, Jin Hongaia, Yu Xinquana, Wang Wangyanga, Tian Weishengb   

  1. a College of Chemistry, Nanchang University, Nanchang 330031;
    b Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2016-08-11 Revised:2016-09-07 Online:2017-01-25 Published:2016-09-12
  • Supported by:

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

C- or O-benzylation of 1,3-dicarbonyl compounds is one of the most fundamental methodologies for carbon-carbon or carbon-oxygen bond formation in organic synthesis.Perfluoroalkanosulfonyl fluoride(RfSO2F) is a class of excellent hy-droxyl-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 C- or O-benzylation of 1,3-dicarbonyl compounds(1,3-diketones and β-ketonic esters) with benzyl alcohols promoted by RfSO2F in alkaline media was explored,and the corresponding C- or O-benzylation products were generated in medium to excellent yields.The optimized reaction conditions:1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) as base,CH2Cl2 as solvent,n-C4F9SO2F,room temperature and the molar ratio of n(1,3-dicarbonyls):n(benzyl alco-hols):n(RfSO2F):n(DBU) is 1.0:1.0:1.0:2.2.A novel reagent system for the direct C- or O-benzylation of 1,3-dicarbonyl compounds with benzyl alcohols was developed.The application scope of RfSO2F in organic synthesis was further broadened.

Key words: perfluoroalkanosulfonyl fluoride, 1,3-dicarbonyl compounds, benzyl alcohols, benzylation