Insights into the Mechanism of Enantioselective Copper‐Catalyzed Ring‐Opening Allylic Alkylation of Cyclopropanols
Akito Kitabayashi, Sho Mizushima, Kosuke Higashida, Yuto Yasuda, Y. Shimizu, Masaya Sawamura
Abstract
Abstract Enantioselective copper‐catalyzed ring‐opening allylic alkylation of a cyclopropanol with an allyl phosphate was developed using a phenol‐NHC chiral ligand. DFT calculations indicated that a copper homoenolate is formed via Li−Cu bimetallic activation of a cyclopropoxide and that syn ‐S N 2’ attack of the Cu center of the homoenolate to the allyl phosphate followed by facile C−C bond formation affords the β‐allylated ketone. Noncovalent interaction analysis showed that the enantiocontrol is achieved by the synergy of electrostatic interactions among Cu, Li, and O atoms, C−H⋅⋅⋅O interactions, and C−H/π London dispersions. magnified image
Topics & Concepts
ChemistryEnantioselective synthesisBimetallic stripAllylic rearrangementCopperTsuji–Trost reactionAlkylationRing (chemistry)CatalysisMedicinal chemistryKetoneLigand (biochemistry)StereochemistryCombinatorial chemistryOrganic chemistryReceptorBiochemistryCyclopropane Reaction MechanismsAsymmetric Hydrogenation and CatalysisN-Heterocyclic Carbenes in Organic and Inorganic Chemistry