Asymmetric (4+1) Annulations by Cascade Allylation and Transient σ‐Alkyl‐Pd(II) Initiated Allylic Csp<sup>3</sup>−H Activation
Haiyu Sun, Hui He, Shao‐Fei Ni, Wusheng Guo
Abstract
Abstract A unique Pd‐catalyzed approach for asymmetric (4+1) annulations via cascade allylation and transient σ‐alkyl‐Pd(II) initiated methylene Csp 3 −H activation is reported. The enolate fragment derived from the decarboxylation of vinyl methylene carbonate is crucial to stabilize the key intermediate. These reactions enable the synthesis of various useful dihydrobenzofurans with excellent enantioselectivity, typically >95 : 5 er , and exclusive ( Z )‐stereoselectivity. Compared with the well‐established annulations via Heck‐type C−H activations, this protocol showcases a conceptually new way to generate σ‐alkyl‐Pd(II) species that could initiate challenging asymmetric Csp 3 −H activations.
Topics & Concepts
Allylic rearrangementDecarboxylationStereoselectivityChemistryAlkylCascadeMethyleneStereochemistryMedicinal chemistryCombinatorial chemistryCatalysisOrganic chemistryChromatographyCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisAsymmetric Synthesis and Catalysis