Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malonates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers
Farbod A. Moghadam, Elliot F. Hicks, Zachary P. Sercel, Alexander Q. Cusumano, Michael D. Bartberger, Brian M. Stoltz
Abstract
An enantioselective iridium-catalyzed allylic alkylation of malonates with trisubstituted allylic electrophiles to form all-carbon quaternary stereocenters is reported. This reaction proceeds at ambient temperature and enables the preparation of a wide range of enantioenriched products in up to 93% yield and 97% ee. The quaternary products can be readily converted to several valuable building blocks such as vicinal quaternary products and β-quaternary acids.
Topics & Concepts
ChemistryStereocenterEnantioselective synthesisAllylic rearrangementTsuji–Trost reactionElectrophileAlkylationCatalysisVicinalQuaternaryQuaternary carbonOrganic chemistryCombinatorial chemistryBiologyPaleontologyAsymmetric Synthesis and CatalysisAsymmetric Hydrogenation and CatalysisAdvanced Synthetic Organic Chemistry