Citation: Yan Zhaohua, Wang Yanmei, Jin Hong'ai, Ai Chengmei, Tian Weisheng. One-Step Enol Esterification of 1, 3-Dicarbonyls with Carboxylic Acids Activated by Perfluoroalkanosulfonyl Fluoride[J]. Chinese Journal of Organic Chemistry, ;2019, 39(7): 2042-2047. doi: 10.6023/cjoc201901012 shu

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

a.
College of Chemistry, Nanchang University, Nanchang 330031
b.
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Yan Zhaohua, yanzh@ncu.edu.cn Tian Weisheng, wstian@sioc.ac.cn
Received Date: 10 January 2019
Revised Date: 24 March 2019
Available Online: 9 July 2019
Fund Project: the National Natural Science Foundation of China 21362022Project supported by the National Natural Science Foundation of China (No. 21362022)

Figures(2)

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 (R_fSO₂F) 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 R_fSO₂F 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(R_fSO₂F):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 R_fSO₂F in organic synthesis was further expanded.
- perfluoroalkanosulfonyl fluoride,
- 1, 3-dicarbonyl compound,
- carboxylic acids,
- enol ester
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