1397116-99-2Relevant academic research and scientific papers
Unprecedented double benzylic rearrangement: Regio- and stereospecific tandem 1,4-shift and Curtin rearrangement
Monta?a, ángel M.,Ponzano, Stefano,Batalla, Consuelo,Font-Bardia, Mercè
, p. 8276 - 8285 (2012)
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.
