Copper-catalyzed 1,4-aminohydroxylation and aminothiolation of 1,3-dienes by carbonyl-assisted migration

We report a copper-catalyzed 1,4-selective aminooxygenation of 1,3-dienes as a direct entry to 1,4-allylic amino alcohols. The reactions are effective on a diverse range of amide-, urea-, and ester-containing 1,3-dienes, allowing for the facile installation of aliphatic alkylamines and free alcohol. The transformation was initiated by a copper-catalyzed electrophilic amination using O-benzoylhydroxylamines, and a carbonyl-assisted oxygen migration delivered the exclusive 1,4-selectivity in the subsequent oxygenation step. Inspired by these mechanistic insights, we also realized an unprecedented 1,4-aminothiolation of thioamide-containing 1,3-dienes by leveraging a novel thiol migration.

Duke Scholars

Author Qiu Wang Chemistry