Toward Efficient and Stereoselective Aromatic and Dearomative Cope Rearrangements: Experimental and Theoretical Investigations of α-Allyl-α'-Aromatic γ-Lactone Derivatives.

The aromatic Cope rearrangement is an elusive transformation that has been the subject of a limited number of investigations compared to those seemingly close analogues, namely the Cope and aromatic Claisen rearrangement. Herein we report our investigations inspired by moderate success observed in the course of pioneering works. By careful experimental and theoretical investigations, we demonstrate that key substitutions on 1,5-hexadiene scaffold allow fruitful transformations. Especially, efficient functionalisation of the heteroaromatic rings results from the aromatic Cope rearrangement, while highly stereoselective interrupted aromatic Cope rearrangements highlight the formation of chiral compounds through a dearomative process.

Organocatalyzed Asymmetric Allylic Alkylation Enables Synthesis of Chiral γ-Lactones Bearing Vicinal Tertiary and Quaternary Stereocenters.

The synthesis of enantioenriched α-aryl-α'-allyl-γ-butyrolactones bearing vicinal tertiary and quaternary stereocenters through organocatalyzed asymmetric allylic alkylation is reported. The process demonstrated that weakly stabilized enolates derived from α-aryl-γ-butyrolactones can undergo regio-, diastereo-, and enantioselective allylation using the proper activation of Morita-Baylis-Hillman (MBH) carbonates.

Organocatalytic enantioselective allylic alkylation of α-aryl γ-lactones: an approach to densely functionalized quaternary stereocentres.

The asymmetric allylic alkylation (AAA) of α-aryl γ-lactones involving the activation of Morita-Baylis-Hillman (MBH) carbonates by an original chiral Lewis base is reported. A wide range of γ-lactones bearing a quaternary stereocentre was thus obtained in both high yields and high enantiomeric ratios. The direct alkylation by MBH alcohol using in situ activation has been also established. Additionally synthetically useful functional transformations of groups surrounding the quaternary stereocentre have been performed.