Enantioselective Synthesis of Skipped Dienes via Iridium-Catalyzed Allylic Alkylation of Phosphonates
Arko Seal, Santanu Mukherjee
Abstract
An enantioselective synthesis of skipped dienes has been developed based on an iridium-catalyzed allylic alkylation of phosphonates and Horner–Wadsworth–Emmons olefination. This two-step protocol uses easily accessible substrates and delivers C2-substituted skipped dienes bearing a C3 stereogenic center, generally with outstanding enantioselectivities (up to 99.5:0.5 er). This is the first catalytic enantioselective allylic alkylation of phosphonates, and the overall process represents a formal enantioselective α-C(sp 2 )–H allylic alkylation of α,β-unsaturated carbonyls and acrylonitrile.
Topics & Concepts
Enantioselective synthesisChemistryStereocenterTsuji–Trost reactionAllylic rearrangementIridiumAlkylationAcrylonitrileCatalysisOrganic chemistryCombinatorial chemistryCopolymerPolymerAsymmetric Hydrogenation and CatalysisAsymmetric Synthesis and CatalysisAdvanced Synthetic Organic Chemistry