American Chemical Society
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Desymmetrization of Cyclohexa-2,5-dienes through a Diastereoselective Protonation−Hydroamination Cascade

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journal contribution
posted on 2006-10-12, 00:00 authored by Raphaël Lebeuf, Frédéric Robert, Kurt Schenk, Yannick Landais
Intramolecular hydroamination of cyclohexa-2,5-dienes led with high selectivity to the corresponding bicyclic allylic amines. This study demonstrates that the reaction does not proceed through a direct hydroamination of one of the diastereotopic olefins but more likely involves a diastereoselective protonation of a pentadienyl anion, followed by addition of a lithium amide across the double bond of the resulting 1,3-diene, and is concluded by a highly regioselective protonation of the final allylic anion.