Probing Trends in Enantioinduction via Substrate Design: Palladium-Catalyzed Decarboxylative Allylic Alkylation of α-Enaminones
Douglas C. Duquette, Alexander Q. Cusumano, Louise Lefoulon, Jared T. Moore, Brian M. Stoltz
Abstract
Herein, we report the palladium-catalyzed decarboxylative asymmetric allylic alkylation of α-enaminones. In addition to serving as valuable synthetic building blocks, we exploit the α-enaminone scaffold and its derivatives as probes to highlight structural and electronic factors that govern enantioselectivity in this asymmetric alkylation reaction. Utilizing the (S)-t-BuPHOX ligand in a variety of nonpolar solvents, the alkylated products are obtained in up to 99% yield and 99% enantiomeric excess.
Topics & Concepts
ChemistryTsuji–Trost reactionAlkylationCatalysisPalladiumYield (engineering)Combinatorial chemistrySubstrate (aquarium)Enantiomeric excessLigand (biochemistry)EnantiomerEnantioselective synthesisOrganic chemistryMaterials scienceGeologyMetallurgyOceanographyReceptorBiochemistrySynthesis and Characterization of PyrrolesAsymmetric Synthesis and CatalysisCatalytic C–H Functionalization Methods