Highly Enantioselective Iridium-Catalyzed Coupling Reaction of Vinyl Azides and Racemic Allylic Carbonates
Min Han, Min Yang, Rui Wu, Yang Li, Tao Jia, Yuanji Gao, Hai‐Liang Ni, Ping Hu, Bi‐Qin Wang, Peng Cao
Abstract
The iridium-catalyzed enantioselective coupling reaction of vinyl azides and allylic electrophiles is presented and provides access to β-chiral carbonyl derivatives. Vinyl azides are used as acetamide enolate or acetonitrile carbanion surrogates, leading to γ,δ-unsaturated β-substituted amides as well as nitriles with excellent enantiomeric excess. These products are readily transformed into chiral N-containing building blocks and pharmaceuticals. A mechanism is proposed to rationalize the chemoselectivity of this coupling reaction.
Topics & Concepts
ChemistryEnantioselective synthesisAllylic rearrangementElectrophileChemoselectivityIridiumCarbanionCatalysisOrganic chemistryEnantiomerCoupling reactionAcetamideCombinatorial chemistryAsymmetric Hydrogenation and CatalysisAdvanced Synthetic Organic ChemistryCatalytic C–H Functionalization Methods