Construction of Vicinal Quaternary Centers via Iridium-Catalyzed Asymmetric Allenylic Alkylation of Racemic Tertiary Alcohols
Mayuko Isomura, David A. Petrone, Erick M. Carreira
Abstract
. This robust catalytic system effects highly enantioconvergent and regioselective alkylation of racemic tertiary α-allenyl alcohols with tetrasubstituted silyl ketene acetals. The transformation displays broad functional group tolerance for both reaction components and allows efficient generation of β-allenyl ester products in good yield and with excellent enantioselectivity. Furthermore, both the allene and ester functionalities were leveraged to upgrade the structural complexity of the products via a series of stereoselective metal-catalyzed functionalization reactions.
Topics & Concepts
ChemistryEnantioselective synthesisPhosphoramiditeRegioselectivityAlkylationIridiumDesymmetrizationVicinalAlleneKeteneOlefin fiberCatalysisSilylationSteric effectsOrganic chemistryCombinatorial chemistryBiochemistryOligonucleotideDNAAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization MethodsSynthetic Organic Chemistry Methods