A two-step protocol for umpolung functionalization of ketones via enolonium species

Shlomy Arava, Shimon Maksymenko, Keshaba Nanda Parida, Gulab K. Pathe, Atul M. More, Yuriy B. Lipisa, Alex M. Szpilman

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2 Scopus citations


α-Functionalization of ketones via umpolung of enolates by hypervalent iodine reagents is an important concept in synthetic organic chemistry. Recently, we have developed a two-step strategy for ketone enolate umpolung that has enabled the development of methods for chlorination, azidation, and amination using azoles. In addition, we have developed C-C bond–forming arylation and allylation reactions. At the heart of these methods is the preparation of the intermediate and highly reactive enolonium species prior to addition of a reactive nucleophile. This strategy is thus reminiscent of the preparation and use of metal enolates in classical synthetic chemistry. This strategy allows the use of nucleophiles that would otherwise be incompatible with the strongly oxidizing hypervalent iodine reagents. In this paper we present a detailed protocol for chlorination, azidation, N-heteroarylation, arylation, and allylation. The products include motifs prevalent in medicinally active products. This article will greatly assist others in using these methods.

Original languageEnglish
Article numbere57916
JournalJournal of Visualized Experiments
Issue number138
StatePublished - 16 Aug 2018


  • Allylation
  • Amination
  • Arylation
  • Chemistry
  • Enolonium species
  • Issue 138
  • Ketone enolates
  • Umpolung


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