级联格氏加成反应：炔丙基克莱森重排用于环己酮中α-联烯季碳中心的立体选择性合成。
Cascade Grignard Addition: Propargyl Claisen Rearrangement for the Stereoselective Synthesis of α-Allene Quaternary Centers in Cyclohexanones.
作者信息
Armendariz-Gonzalez Estefania, Saputra Adi, Mureka Edward W, Locicero Cale M, Womble Gabrielle L, Tan Gloria, Watson Abigail A, Fronczek Frank R, Kartika Rendy
机构信息
232 Choppin Hall, Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, United States.
出版信息
Org Lett. 2025 Jul 25;27(29):7767-7772. doi: 10.1021/acs.orglett.5c02006. Epub 2025 Jun 18.
We report a new method for the enantio- and diastereoselective synthesis of α-allene quaternary centers in fully substituted cyclohexanones at the α-positions. This reaction involves asymmetric 1,2-carbonyl addition to 2--propargyl enones using a mixture of Grignard reagents and the PMP-H8-BINOL ligand. The resulting magnesium alkoxide chelate intermediate then activated the propargyl vinyl ether moiety, thereby triggering a cascade propargyl Claisen rearrangement in a diastereoselective manner. The synthetic applications of this method in the context of complex molecules are also demonstrated.
我们报道了一种在α-位完全取代的环己酮中对映选择性和非对映选择性合成α-丙二烯季碳中心的新方法。该反应涉及使用格氏试剂和PMP-H8-BINOL配体的混合物对2-炔丙基烯酮进行不对称1,2-羰基加成。生成的醇镁螯合中间体随后激活炔丙基乙烯基醚部分，从而以非对映选择性的方式引发级联炔丙基克莱森重排。本文还展示了该方法在复杂分子合成中的应用。
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