Ah ighly enantioselective kinetic resolution of tertiary 2-alkoxycarboxamido allylic alcohols has been achieved through ac hiral phosphoric acid catalyzed intramolecular transesterification reaction. Both alkyl,aryl-and dialkylsubstituted tertiary allylic alcohols were resolved with excellent efficiencies,affording both the recovered tertiary alcohols and the carbamate products with high enantioselectivities (with sf actors up to 164.6). Ag ram-scale reaction with 1mol % catalyst loading and the facile conversion of the enantioenriched products into useful chiral building blocks,s uch as chiral oxazolidinones and b-amino alcohols,d emonstrate the value of this reaction.

An efficient protocol for kinetic resolution of tertiary alcohols has been developed through an unprecedented asymmetric enamide‐imine tautomerism process enabled by chiral phosphoric acid catalysis. A broad range of racemic 2‐arylsulfonamido tertiary allyl alcohols could be kinetically resolved with excellent kinetic resolution performances (with s‐factor up to >200). This method is particularly effective for a series of 1,1‐dialkyl substituted allyl alcohols, which produced chiral tertiary alcohols that would be difficult to access via other asymmetric methods. Facile and versatile transformations of the chiral α‐hydroxy imine and enamide products, especially the efficient stereodivergent synthesis of all four stereoisomers of β‐amino tertiary alcohols using one enantiomer of the catalyst, demonstrated the value of this kinetic resolution method.

A novel asymmetric synthesis of dihydropyridinones with vicinal quaternary stereocenters has been realized by asymmetric aza-Diels−Alder reactions of 3-amido allylic alcohols with oxazolones enabled by chiral phosphoric acid catalysis. A series of aryl/alkyl-and alkyl/alkyl-disubstituted 3-amido allylic tertiary alcohols and 4-substituted oxazolones could be well tolerated in these reactions, producing dihydropyridinones with excellent diastereoselectivities and high enantioselectivities. Mechanistic study and control experiments were performed to shed light on the reaction mechanism, in which a configurationally defined β,β-disubstituted α,β-unsaturated N−H ketimine was proposed as the key intermediate.

Ah ighly enantioselective kinetic resolution of tertiary 2-alkoxycarboxamido allylic alcohols has been achieved through ac hiral phosphoric acid catalyzed intramolecular transesterification reaction. Both alkyl,aryl-and dialkylsubstituted tertiary allylic alcohols were resolved with excellent efficiencies,affording both the recovered tertiary alcohols and the carbamate products with high enantioselectivities (with sf actors up to 164.6). Ag ram-scale reaction with 1mol % catalyst loading and the facile conversion of the enantioenriched products into useful chiral building blocks,s uch as chiral oxazolidinones and b-amino alcohols,d emonstrate the value of this reaction.