Iridium-Catalyzed Remote Site-Switchable Hydroarylation of Alkenes Controlled by Ligands |
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Authors: | Fei Li Yicong Luo Jinbao Ren Dr Qianjia Yuan Prof Dr Deyue Yan Prof Dr Wanbin Zhang |
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Institution: | Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China |
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Abstract: | An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering the products functionalized at the subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields and with good to excellent site-selectivities. The catalytic system showed good functional group tolerance and a broad substrate scope, including unactivated and activated alkenes. More importantly, the regioconvergent transformations of mixtures of isomeric alkenes were also successfully realized. The results of the mechanistic studies demonstrate that the reaction undergoes a chain-walking process to give an Ar−Ir−H] complex of terminal alkene. The subsequent processes proceed through the modified Chalk–Harrod-type mechanism via the migratory insertion of terminal alkene into the Ir−C bond followed by C−H reductive elimination to afford the hydrofunctionalization products site-selectively. |
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Keywords: | Alkene Mixtures Chain-Walking Iridium Regioconvergence Site-Selectivity |
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