Department of Chemistry, University of Chicago, Chicago, IL 60637, USA.
Science. 2021 Nov 5;374(6568):734-740. doi: 10.1126/science.abl7854. Epub 2021 Nov 4.
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.
迄今为止，在给定的分子骨架内选择性迁移羰基氧，尤其是迁移到相邻的碳上，仍然具有挑战性。在这项工作中，我们描述了一种简单的一锅或两锅法将酮转化为顺式碳。该方法首先将酮转化为相应的烯基三氟甲磺酸酯，然后在双功能氢氮供体的作用下，通过钯和降冰片烯催化的区域选择性α-氨基化和反位氢化来实现。得到的“换位烯胺”中间体随后可以水解得到 1,2-羰基迁移产物。该方法通过后期官能化可以快速获得不常见的生物活性类似物。
