The catalytic asymmetric borylation of conjugated carbonyls followed by stereoselective intramolecular cascade cyclizations with in situ generated chiral enolates are extremely rare. Herein, we report the enantioselective Cu(I)-catalyzed β-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones. This asymmetric desymmetrization strategy has a broad range of substrate scope to generate densely functionalized bicyclic enones bearing four contiguous stereocenters with excellent yield, enantioselectivity, and diastereoselectivity. One-pot borylation/cyclization/oxidation via the sequential addition of sodium perborate reagent affords the corresponding alcohols without affecting yield and enantioselectivity. The synthetic potential of this reaction is explored through gram-scale reactions and further chemoselective transformations on products. DFT calculations explain the requirement of the base in an equimolar ratio in the reaction, as it leads to the formation of a lithium-enolate complex to undergo C-C bond formation via a chair-like transition state, with a barrier that is 22.5 kcal/mol more favourable than that of the copper-enolate complex.

Enantioselective desymmetrization of prochiral 1,3cyclodiketones is the most convenient and highly desired transformation to access densely functionalized, enantiomerically enriched scaffolds with multiple chiral centers. In recent years, organocatalysis has made significant progress in this research area along with other traditional metal-or enzymecatalyzed reactions. This mini-review provides an overview of the recent developments in the domain of organocatalytic enantioselective desymmetrization along with a brief discussion about future perspectives.

An efficient, mild, and transition-metal free formal C(sp2)−H arylation of prochiral 2,2-disubstituted cyclopentene-1,3-diones is reported. This oxidative arylation with β-naphthols proceeds via base-mediated C-Michael addition followed by aerial oxygen insertion...