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Synthesis 2011(15): 2372-2376  
DOI: 10.1055/s-0030-1260085
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Selective Electrochemical Fluorodesulfurization of Benzo- and Pyrido-Fused Oxazine Derivatives Using Ex-cell Halogen Mediators

Bin Yin, Shinsuke Inagi, Toshio Fuchigami*
Department of Electronic Chemistry, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
Fax: +81(45)9245406; e-Mail: fuchi@echem.titech.ac.jp;
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Publication History

Received 15 April 2011
Publication Date:
21 June 2011 (online)

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Abstract

Although the direct anodic fluorination of 3-phenyl-2H-1,4-benzoxazine was not very effective, the fluorodesulfurization of 3-aryl-2-(phenylsulfanyl)-2H-1,4-benzoxazines using various anodically generated halogen mediators in the presence of triethyl­amine tris(hydrogen fluoride) by an ex-cell method efficiently and selectively provided the corresponding monofluorinated products. In sharp contrast, in-cell halogen mediators did not work well. Furthermore, the selective fluorodesulfurization of pyrido[3,2-b][1,4]oxazine derivatives was also successfully carried out using the same ex-cell method to provide the corresponding monofluorinated products in moderate yields.

Key words

halogenation - fluorine - heterocycles - electron transfer - oxidations

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21

When 0.5 equivalent of molecular iodine were used under the ex-cell method conditions, the corresponding monofluorinated product 4a was obtained in only 45% yield.