Electrolytic partial fluorination of organic compounds. 83. Anodic fluorination of N-substituted pyrroles and its synthetic applications to gem-difluorinated heterocyclic compounds

Toshiki Tajima, Atsushi Nakajima, Toshio Fuchigami

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20 Citations (Scopus)

Abstract

Anodic fluorination of N-substituted pyrroles was carried out in MeCN containing supporting fluoride salts such as Et3N-nHF (n = 2-5) and Et4NF-4HF with use of platinum electrodes under constant current conditions. Anodic fluorination of N-methyl- and N-p-tosylpyrroles having an electron-withdrawing cyano group proceeded smoothly to provide the corresponding fluorinated products in moderate to excellent yields, while anodic fluorination of N-methylpyrrole devoid of an electron-withdrawing cyano group did not take place and a polymeric product was formed at the anode surface. In sharp contrast to the cases of N-methylpyrroles, even N-p-tosylpyrrole devoid of an electron-withdrawing cyano group underwent anodic fluorination efficiently. Diels-Alder reaction of 5,5-difluoro-1-methyl-3-pyrrolin-2-one (2e) derived from anodic fluorination of 2-cyano-1-methylpyrrole (2a) with various dienes was carried out to provide the cycloaddition products in excellent yields. Furthermore, Michael reaction of 2e with various nucleophiles was also successfully carried out to provide the Michael addition products in good to excellent yields.

Original languageEnglish
Pages (from-to)1436-1441
Number of pages6
JournalJournal of Organic Chemistry
Volume71
Issue number4
DOIs
Publication statusPublished - 2006 Feb 17
Externally publishedYes

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Gems
Heterocyclic Compounds
Fluorination
Pyrroles
Organic compounds
Electrons
Nucleophiles
Cycloaddition
Platinum
Fluorides
Anodes
Salts
Electrodes
N-methylpyrrole

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Electrolytic partial fluorination of organic compounds. 83. Anodic fluorination of N-substituted pyrroles and its synthetic applications to gem-difluorinated heterocyclic compounds",
abstract = "Anodic fluorination of N-substituted pyrroles was carried out in MeCN containing supporting fluoride salts such as Et3N-nHF (n = 2-5) and Et4NF-4HF with use of platinum electrodes under constant current conditions. Anodic fluorination of N-methyl- and N-p-tosylpyrroles having an electron-withdrawing cyano group proceeded smoothly to provide the corresponding fluorinated products in moderate to excellent yields, while anodic fluorination of N-methylpyrrole devoid of an electron-withdrawing cyano group did not take place and a polymeric product was formed at the anode surface. In sharp contrast to the cases of N-methylpyrroles, even N-p-tosylpyrrole devoid of an electron-withdrawing cyano group underwent anodic fluorination efficiently. Diels-Alder reaction of 5,5-difluoro-1-methyl-3-pyrrolin-2-one (2e) derived from anodic fluorination of 2-cyano-1-methylpyrrole (2a) with various dienes was carried out to provide the cycloaddition products in excellent yields. Furthermore, Michael reaction of 2e with various nucleophiles was also successfully carried out to provide the Michael addition products in good to excellent yields.",
author = "Toshiki Tajima and Atsushi Nakajima and Toshio Fuchigami",
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T1 - Electrolytic partial fluorination of organic compounds. 83. Anodic fluorination of N-substituted pyrroles and its synthetic applications to gem-difluorinated heterocyclic compounds

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AU - Nakajima, Atsushi

AU - Fuchigami, Toshio

PY - 2006/2/17

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AB - Anodic fluorination of N-substituted pyrroles was carried out in MeCN containing supporting fluoride salts such as Et3N-nHF (n = 2-5) and Et4NF-4HF with use of platinum electrodes under constant current conditions. Anodic fluorination of N-methyl- and N-p-tosylpyrroles having an electron-withdrawing cyano group proceeded smoothly to provide the corresponding fluorinated products in moderate to excellent yields, while anodic fluorination of N-methylpyrrole devoid of an electron-withdrawing cyano group did not take place and a polymeric product was formed at the anode surface. In sharp contrast to the cases of N-methylpyrroles, even N-p-tosylpyrrole devoid of an electron-withdrawing cyano group underwent anodic fluorination efficiently. Diels-Alder reaction of 5,5-difluoro-1-methyl-3-pyrrolin-2-one (2e) derived from anodic fluorination of 2-cyano-1-methylpyrrole (2a) with various dienes was carried out to provide the cycloaddition products in excellent yields. Furthermore, Michael reaction of 2e with various nucleophiles was also successfully carried out to provide the Michael addition products in good to excellent yields.

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