Abstract
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 alpha-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 degrees 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 language | English |
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Journal | Angewandte chemie-international edition |
Volume | 56 |
Pages (from-to) | 2599-2603 |
ISSN | 1433-7851 |
DOIs | |
Publication status | Published - 2017 |
Keywords
- allylation
- enolonium species
- ketones
- polarity inversion
- umpolung