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Enolonium Species—Umpoled Enolates
Author(s) -
Arava Shlomy,
Kumar Jayprakash N.,
Maksymenko Shimon,
Iron Mark A.,
Parida Keshaba N.,
Fristrup Peter,
Szpilman Alex M.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201610274
Subject(s) - hypervalent molecule , regioselectivity , chemistry , silanes , yield (engineering) , medicinal chemistry , stereochemistry , organic chemistry , iodine , catalysis , silane , materials science , metallurgy
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.