Gurak John A, Engle Keary M
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Rd., La Jolla, California 92037, United States.
ACS Catal. 2018 Oct 5;8(10):8987-8992. doi: 10.1021/acscatal.8b02717. Epub 2018 Aug 24.
The hydroarylation of alkenes is an attractive approach to construct carbon-carbon (C-C) bonds from abundant and structurally diverse starting materials. Herein we report a palladiumcatalyzed reductive Heck hydroarylation of unactivated and heteroatom-substituted terminal alkenes with an array of (hetero)aryl iodides. The reaction is anti-Markovnikov selective and tolerates a wide variety of functional groups on both the alkene and (hetero)aryl coupling partners. Additionally, applications of this method to complex molecule diversifications were demonstrated. Deuteriumlabeling experiments are consistent with a mechanism in which the key alkylpalladium(II) intermediate is intercepted with formate and undergoes a decarboxylation/C-H reductive elimination cascade to afford the saturated product and turn over the cycle.
烯烃的氢芳基化反应是一种极具吸引力的方法，可从丰富且结构多样的起始原料构建碳-碳（C-C）键。在此，我们报道了一种钯催化的未活化和杂原子取代的末端烯烃与一系列（杂）芳基碘化物的还原Heck氢芳基化反应。该反应具有反马氏选择性，并且对烯烃和（杂）芳基偶联伙伴上的多种官能团都具有耐受性。此外，还展示了该方法在复杂分子多样化中的应用。氘标记实验与一种机理一致，即关键的烷基钯（II）中间体与甲酸酯发生截获，并经历脱羧/C-H还原消除级联反应，以提供饱和产物并使循环得以周转。
