Executive Summary : | Synthesis of highly functionalized and optically active carbocycles is an attractive target in synthetic organic chemistry due to their prevalence in several natural products, bioactive compounds and materials. In this regard, catalytic enantioselective desymmetrization of prochiral cyclic 1,3-diones and their derivatives is one of the most efficient and convenient approaches to access these scaffolds. In addition, stereoselective installation of all-carbon quaternary stereogenic center(s) on carbocycles, which are otherwise difficult to achieve by conventional methods, can easily be accomplished using asymmetric desymmetrization of 2,2-disubstituted cyclic 1,3-diones and their prochiral derivatives having pre-existing prochiral quaternary carbon centre. We have recently designed a new class of C2-symmetric cyclopentadiene-1,3-dicarbonitrile from 2,2-disubstituted cyclopentane-1,3-diones, which could open a new era for various enantioselective desymmetrization approaches to access complex molecules with multiple stereocenters. Several research groups are actively involved in the desymmetrization of the prochiral dienones using organocatalysis since last two decades. However, the transition-metal catalyzed enantioselective desymmetrization of these molecules is still a significant challenge in the organic chemistry and very limited number of reports appeared. Therefore, the basic idea of this proposal is to develop general diastereo- and enantioselective desymmetrization approaches on various C2-symmetric 1,3-diones and their new prochiral derivatives and their applications in the synthesis of natural products and biologically important molecules. Herein, we demonstrate the potential of transition-metal catalysis in the enantioselective desymmetrization of prochiral molecules such as 2,2-disubstituted cyclopentane-1,3-diones, bis-triflates and cyclic 1,3-dicarbonitrile to access highly functionalized complex carbocycles. |