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Chinese Journal of Organic Chemistry >

2024 , Vol. 44 >Issue 4: 1226 - 1239

DOI: https://doi.org/10.6023/cjoc202311001

ARTICLES

[3+2] Cyclization of Difluoroacetohydrazonoyl Bromides with β-(N,N-Dimethylamino)enones/Enoates/Enamides

  • Xiaoyong Li ,
  • Danfeng Huang ,
  • Yuxiu Zhou ,
  • Xiaokang Liu ,
  • Kehu Wang ,
  • Junjiao Wang ,
  • Yulai Hu
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  • College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070
* E-mail: ;

Received date: 2023-11-01

  Revised date: 2023-12-11

  Online published: 2023-12-29

Supported by

National Natural Science Foundation of China(22061037); National Natural Science Foundation of China(21861033); Shanghai Sinofluoro Chemicals Co., Ltd

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Abstract

A [3+2] cyclization of difluoromethyl nitrile imines generated in situ from difluoroacetohydrazonoyl bromides with β-(N,N-dimethylamino)enones/enoates/enamides in the presence of base is described. The cycloaddition reaction pro- duced the pyrazoline intermediates, from which 3,4-disubstituted-3-difluoromethylpyrazoles were obtained in moderate to good yields via spontaneous elimination of the Me2NH molecule. The reaction is fully regioseclective by the interaction of lowest unoccupied molecular orbital (LUMO) of the 1,3-dipoles and highest occupied molecular orbital (HOMO) of electron-rich alkenes (inverse-electron-demand). This approach expands the types of [3+2] cyclization involved difluoro- methyl nitrile imines, which provides a simple, efficient and novel method for the synthesis of 3-difluoromethylpyrazoles.

Key words： 3-difluoromethylpyrazoles; difluoroacetohydrazonoyl bromides; [3+2] cyclization; regioselectivity

Cite this article

Xiaoyong Li , Danfeng Huang , Yuxiu Zhou , Xiaokang Liu , Kehu Wang , Junjiao Wang , Yulai Hu . [3+2] Cyclization of Difluoroacetohydrazonoyl Bromides with β-(N,N-Dimethylamino)enones/Enoates/Enamides[J]. Chinese Journal of Organic Chemistry, 2024 , 44(4) : 1226 -1239 . DOI: 10.6023/cjoc202311001

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