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Remote Stereocontrol of All-Carbon Quaternary Centers via Cobalt-Catalyzed Asymmetric Olefin Isomerization

Xianle Rong, Jie Yang, Shihan Liu, Yu Lan, Qiang Liu

2023CCS Chemistry21 citationsDOIOpen Access PDF

Abstract

Open AccessCCS ChemistryCOMMUNICATIONS23 Jan 2023Remote Stereocontrol of All-Carbon Quaternary Centers via Cobalt-Catalyzed Asymmetric Olefin Isomerization Xianle Rong, Jie Yang, Shihan Liu, Yu Lan and Qiang Liu Xianle Rong , Jie Yang , Shihan Liu , Yu Lan and Qiang Liu https://doi.org/10.31635/ccschem.023.202202616 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Asymmetric olefin isomerization has become a powerful tool for positional migration of C=C double bonds to afford valuable chiral olefins. However, the synthesis of optically active all-carbon quaternary stereocenters via this strategy is still rare. Herein, we report a cobalt-catalyzed desymmetric olefin isomerization to access 1-methylcyclohexenes bearing β-quaternary stereocenters in a chemo-, site- and stereoselective fashion. Preliminary mechanistic studies revealed the Co-H insertion/β-H elimination reaction pathway and the origin of remote stereocontrol of all-carbon quaternary centers. The gram-scale synthesis and stereoretentive transformations of spirocyclic products demonstrate the synthetic utility of this reaction. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 0Issue jaPage: 1-235Supporting Information Copyright & Permissions© 2023 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...

Topics & Concepts

StereocenterIsomerizationOlefin fiberStereochemistryChemistryQuaternary carbonCatalysisStereoselectivityCombinatorial chemistryEnantioselective synthesisOrganic chemistryCatalytic C–H Functionalization MethodsSynthetic Organic Chemistry MethodsAsymmetric Synthesis and Catalysis