Unprecedented double benzylic rearrangement: regio- and stereospecific tandem 1,4-shift and Curtin rearrangement |
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Authors: | Ángel M. Montaña Stefano Ponzano Consuelo Batalla Mercè Font-Bardia |
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Affiliation: | 1. Industrial and Applied Organic Chemistry Research Unit, Department of Organic Chemistry, University of Barcelona, c/Martí i Franquès 1-11, 08028 Barcelona, Spain;2. Department of Crystallography, Mineralogy and Mineral Deposits, University of Barcelona, c/Martí i Franquès s/n, 08028 Barcelona, Spain;3. Unitat de Difracció RX, Centre Cientific i Tecnològic (CCiTUB), Universitat de Barcelona, c/Solé Sabarís 1-3, 08028 Barcelona, Spain |
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Abstract: | An α-benzyloxyketone forming part of a strained cyclopentane carbon framework when treated with 10 equiv of anhydrous NaOH in absolute ethanol, for 2 h, affords in a 65% yield a new 2-benzyl-2-hydroxyketone, resulting from an unprecedented double benzylic rearrangement. This new rearrangement could be interpreted as an initial benzylic 1,4-shift between the O-enolate alkoxide of the ketone group and the oxygen atom of the benzyloxy ether, followed by a Curtin type benzylic 1,2-shift. Apart from the novelty and the synthetic application of this transformation it is worth noting the complete regio- and stereoselectivity observed. The structures of both substrate and product have been confirmed by X-ray diffraction studies. A tentative mechanism is herein proposed. |
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