Enolonium Species—Umpoled Enolates

Shlomy Arava, Jayprakash N. Kumar, Shimon Maksymenko, Mark A. Iron, Keshaba N. Parida, Peter Fristrup, Alex M. Szpilman

Research output: Contribution to journalArticlepeer-review

72 Scopus citations


Enolonium species/iodo(III)enolates of carbonyl compounds have been suggested to be intermediates in a wide variety of hypervalent iodine induced chemical transformations of ketones, including α-C−O, α-C−N, α-C−C, and α-carbon–halide bond formation, but they have never been characterized. We report that these elusive umpoled enolates may be made as discrete species that are stable for several minutes at −78 °C, and report the first spectroscopic identification of such species. It is shown that enolonium species are direct intermediates in C−O, C−N, C−Cl, and C−C bond forming reactions. Our results open up chemical space for designing a variety of new transformations. We showcase the ability of enolonium species to react with prenyl, crotyl, cinnamyl, and allyl silanes with absolute regioselectivity in up to 92 % yield.

Original languageEnglish
Pages (from-to)2599-2603
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number10
StatePublished - 1 Mar 2017


  • allylation
  • enolonium species
  • ketones
  • polarity inversion
  • umpolung


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