Plausible Pnicogen Bonding of epi-Cinchonidine as a Chiral Scaffold in Catalysis

As a non-covalent interaction of a chiral scaffold in catalysis, pnicogen bonding of epi-cinchonidine (epi-CD), a cinchona alkaloid, was simulated to consider whether the interaction can have the potential controlling enantiotopic face like hydrogen bonding. Among five reactive functional groups in...

Descripción completa

Detalles Bibliográficos
Autores principales: Ullah, Zakir, Kim, Kang, Venkanna, Arramshetti, Kim, Hye su, Kim, Moon Il, Kim, Mi-hyun
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8290064/
https://www.ncbi.nlm.nih.gov/pubmed/34295874
http://dx.doi.org/10.3389/fchem.2021.669515
Descripción
Sumario:As a non-covalent interaction of a chiral scaffold in catalysis, pnicogen bonding of epi-cinchonidine (epi-CD), a cinchona alkaloid, was simulated to consider whether the interaction can have the potential controlling enantiotopic face like hydrogen bonding. Among five reactive functional groups in epi-CD, two stable complexes of the hydroxyl group (X-epi-CD1) at C(17) and of the quinoline ring (X-epi-CD2) at N(16) with pnictide family analytes [X = substituted phosphine (PX), i.e., F, Br, Cl, CF(3), CN, HO, NO(2), and CH(3), and pnictide family analytes, i.e., PBr(3), BiI(3), SbI(3), and AsI(3)] were predicted with intermolecular interaction energies, charge transfer (Q(Mulliken) and Q(NBO)), and band gap energies of HOMO–LUMO (Eg) at the B3LYP/6-31G(d,p) level of density functional theory. It was found that the dominant site of pnicogen bonding in epi-CD is the quinoline ring (N(16) atom) rather than the hydroxyl group (O(36) atom). In addition, the UV-Vis spectra of the complex were calculated by time-dependent density functional theory (TD-DFT) at the B3LYP/6-31+G(d,p) level and compared with experimental measurements. Through these calculations, two intermolecular interactions (H-bond vs. pnicogen bond) of epi-CD were compared.