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.

The enantioselective desymmetrization via remote C(sp 2 )−H amidation of the prochiral 2,2-disubstituted cyclopentene-1,3-dione with N-methoxybenzamide has been developed. The overall process was catalyzed by a chiral bifunctional thiourea catalyst through a sequential conjugate-additioneliminationtautomerization. This strategy provides rapid access to highly functionalized five-membered carbocycles, bearing an all-carbon quaternary stereogenic center through remote stereocontrol in high yields with moderate to excellent enantioselectivities.

Herein we have reported the palladium(0)catalyzed decarboxylative oxa-Michael addition/remote α-allylation/1,3-migration of prochiral allyl carbonate-tethered cyclohexadienones in good yields. This unconventional intramolecular rearrangement is triggered by the base-mediated retro-Michael ring-opening reaction (β-elimination) and subsequent syn-selective oxa-Michael addition on the less substituted enone functionality. The generality of tandem decarboxylative allylation was examined with various substrates and in the gram-scale reaction.