To date, it remains challenging to selectively migrate a carbonyl oxygen within a given molecular scaffold, especially to an adjacent carbon. In this work, we describe a simple one- or two-pot protocol that transposes a ketone to the vicinal carbon. This approach first converts the ketone to the corresponding alkenyl triflate, which can then undergo the palladium- and norbornene-catalyzed regioselective α-amination and ipso-hydrogenation enabled by a bifunctional hydrogen and nitrogen donor. The resulting “transposed enamine” intermediate can subsequently be hydrolyzed to produce the 1,2-carbonyl–migrated product. This method allows rapid access to unusual bioactive analogs through late-stage functionalization.

中文翻译：

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通过三氟甲磺酸酯介导的 α-胺化进行羰基 1,2-转座

迄今为止，在给定的分子支架内选择性迁移羰基氧仍然具有挑战性，尤其是迁移到相邻的碳。在这项工作中，我们描述了一个简单的一锅或两锅协议，将酮转移到邻位碳上。这种方法首先将酮转化为相应的三氟甲磺酸链烯基酯，然后可以通过双功能氢和氮供体进行钯和降冰片烯催化的区域选择性 α-胺化和同位氢化。生成的“转位烯胺”中间体随后可以水解生成 1,2-羰基迁移产物。这种方法允许通过后期功能化快速获得不寻常的生物活性类似物。