Among the unstabilized enolates used as nucleophile in iridium-catalyzed asymmetric allylic alkylation reactions, amide enolates are least explored. Vinyl azides are now employed as amide enolate surrogate for the first time in Ir-catalyzed asymmetric allylic alkylation with branched allylic alcohols as the allylic electrophile. Competing reaction pathways are suppressed through systematic tuning of steric and electronic properties of vinyl azide to effect α-allylic alkylation of secondary acetamides with high atom-economy, exclusive branched selectivity and moderate to excellent enantioselectivity.
Iridium-Catalyzed Asymmetric α-Allylic Alkylation of Amides using Vinyl Azide as Amide Enolate Surrogate
06 August 2020, Version 1
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