Enantioselective Annulation Reactions of Bisenolates Prepared Through Dearomatization Reactions of Aromatic and Heteroaromatic Diesters

Abstract A one‐pot, enantioselective strategy for the dearomatization–annulation of aromatic diesters to give a range of highly functionalized polycyclic molecules with excellent enantioselectivity is presented. This methodology is based on the reaction of bisenolates, prepared by treating aromatic diesters with trialkyltin lithium reagents, which involves a stanna‐Brook rearrangement, with 1,ω‐dihaloalkanes and other biselectrophiles. We have also developed experimental conditions for performing these reactions with substoichiometric amounts of the required tin reagent by in situ recycling of Me 6 Sn 2 into Me 3 SnLi with excess lithium metal, and provide a study of the scope and limitations of this synthetic methodology.