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Chiral Bicyclo[2.2.2]octane‐Fused CpRh Complexes: Synthesis and Potential Use in Asymmetric C−H Activation

Guozhu Li, Xiao Yan, Ji‐Jun Jiang, Hao Liang, Chao Zhou, Jun Wang

2020Angewandte Chemie International Edition72 citationsDOI

Abstract

Abstract A new class of chiral cyclopentadienyl rhodium(I) complexes (CpRh I ) bearing C 2 ‐symmetric chiral bridged‐ring‐fused Cp ligands was prepared. The complexes were successfully applied to the asymmetric C−H activation reaction of N ‐methoxybenzamides with quinones, affording a series of chiral hydrophenanthridinones in up to 82 % yield with up to 99 % ee . Interestingly, structure analysis reveals that the side wall of the optimal chiral CpRh I catalyst is vertically more extended, horizontally less extended, and closer to the metal center in comparison with the classic binaphthyl and spirobiindanyl CpRh I complexes, and may thus account for its superior catalytic performance.

Topics & Concepts

Cyclopentadienyl complexOctaneRhodiumChemistryBicyclic moleculeCatalysisYield (engineering)Enantioselective synthesisStereochemistryAsymmetric hydrogenationRing (chemistry)MetalOrganic chemistryMaterials scienceMetallurgyCatalytic C–H Functionalization MethodsCyclopropane Reaction MechanismsOrganometallic Complex Synthesis and Catalysis
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