Dinuclear Zn-Catalytic System as Brønsted Base and Lewis Acid for Enantioselectivity in Same Chiral Environment

Zinc (Zn) is a crucial element with remarkable significance in organic transformations. The profusion of harmless zinc salts in the Earth's outer layer qualifies zinc as a noteworthy contender for inexpensive and eco-friendly reagents and catalysts. Recently, widely recognized uses of organo-Zn compounds in the field of organic synthesis have undergone extensive expansion toward asymmetric transformations. The ProPhenol ligand, a member of the chiral nitrogenous-crown family, exhibits the spontaneous formation of a dual-metal complex when reacted with alkyl metal (R-M) reagents, e.g., ZnEt₂. The afforded Zn complex possesses two active sites, one Lewis acid and the other Brønsted base, thereby facilitating the activation of nucleophiles and electrophiles simultaneously within the same chiral pocket. In this comprehensive analysis, we provide a thorough account of the advancement and synthetic potential of these diverse catalysts in organic synthesis, while emphasizing the reactivity and selectivities, i.e., dr and ee due to the design/structure of the ligands employed.