The enantioselective synthesis of 2-indolyl-1-nitro derivatives and BODIPY dyes in the presence of chiral bifunctional squaramide organocatalysts

Dündar, Esra
In our research group, chiral bifunctional squaramides with different basic units have been synthesized and evaluated in various asymmetric reactions. To test the catalytic activity of organocatalysts, Friedel-Crafts alkylation of indoles with nitroolefins was selected as a model reaction in the first part of the study. 19 different 2-indolyl-1-nitro derivatives were synthesized with up to >99% ee in the presence of sterically encumbered tert-butyl substituted squaramide/quinine. Besides, 2-adamantyl squaramide/quinine was evaluated in the addition of BODIPY core to isatin derivatives which will be the first example of this kind of enantioselective addition in literature. 6 novel chiral BODIPY dyes were synthesized with up to 60% ee, and their spectroscopic and chiroptical properties were investigated. In the final chapter, a point chiral at boron and carbon BODIPY was synthesized with a two-pot, one-step synthesis-an interrupted Knoevenagel condensation. ECD spectra of the dye showed a strong Cotton effect in the visible region. However, this dye showed weak fluorescence emission due to partly vibrational relaxations and bent-shaped molecular geometry.


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The chemical shift of the N(2)(CH3)(4) ion, which has been found to exhibit the similar anomalous behavior of the monoclinic angle $\Delta \beta $ , was related to the order parameter to evaluate the temperature dependence of the linewidth (damping constant) for N-14 nuclear magnetic resonance spectrum of this crystal in terms of the dynamic Ising models, namely the pseudospin-phonon-coupled (PS) and the energy fluctuation (EF) models. The results from both PS and EF models were successful to explain the ab...
Citation Formats
E. Dündar, “The enantioselective synthesis of 2-indolyl-1-nitro derivatives and BODIPY dyes in the presence of chiral bifunctional squaramide organocatalysts,” Ph.D. - Doctoral Program, Middle East Technical University, 2022.