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.

中文翻译：

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铜催化的 1,4-氨基羟基化反应和羰基辅助迁移对 1,3-二烯的氨基硫醇化反应


我们报道了 1,3-二烯的铜催化 1,4-选择性氨氧反应作为 1,4-烯丙基氨基醇的直接进入。该反应对各种含酰胺、尿素和酯的 1,3-二烯有效，允许脂肪族烷基胺和游离醇的轻松安装。该转化是使用 O-苯甲酰羟胺的铜催化亲电胺化引发的，羰基辅助氧迁移在随后的氧合步骤中提供了独特的 1,4-选择性。受这些机理见解的启发，我们还通过利用一种新型硫醇迁移实现了前所未有的含硫酰胺的 1,3-二烯的 1,4-氨基硫醇化。