Executive Summary : | "The synthesis of biologically and pharmacologically important organic compounds is challenging due to the difficulty of halogenation of unactivated strong C(sp³)-H bonds under mild conditions. The biosynthesis process involves alpha-KG-dependent non-heme iron enzymes, heme protein chlorperoxidase (CPO), and non-heme proteins like SyrB2 halogenate sp³ C-H bonds of the substrate selectively via the formation of chloroferryl species. Research has been conducted to develop synthetic biomimetic catalysts for alkane halogenation, but the major concern is the formation of unwanted hydroxylated products during the synthesis of halogenated products. Recently, Ni(II) complexes supported by amido-quinoline ligands have been reported, which effectively catalyze C-H chlorination of strong C-H bonds, giving exclusively chlorinated products without any hydroxylated products, mimicking the activity of halogenase enzymes. However, enantioselective incorporation of halogen atoms to a stereogenic center of a hydrocarbon using 3d transition metal catalysts is still a rare and vastly unexplored area of research.
The proposed research plan will investigate the design, synthesis, and characterization of 3d transition metal (TSM) complexes of amido-oxazoline ligands (L1-L10), as well as the stability and reactivity of these complexes in water/organic solvents. The enantiomeric excess (ee%) will be measured by HPLC analysis on a chiral stationary phase. The preparation and characterization of [MIII(F)L] for fluorination will be carried out, and the reactivity of [MIII(F)L] as a potent oxidant in the presence of AgF will be monitored by UV-Vis spectroscopy." |