Ullah Zakir, Kim Kang, Venkanna Arramshetti, Kim Hye Su, Kim Moon Il, Kim Mi-Hyun
Department of Pharmacy, College of Pharmacy, Gachon Institute of Pharmaceutical Science, Gachon University, Incheon, South Korea.
Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon, South Korea.
Front Chem. 2021 Jul 6;9:669515. doi: 10.3389/fchem.2021.669515. eCollection 2021.
As a non-covalent interaction of a chiral scaffold in catalysis, pnicogen bonding of cinchonidine (), 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 , two stable complexes of the hydroxyl group (X-epi-CD1) at C and of the quinoline ring (X-epi-CD2) at N with pnictide family analytes [X = substituted phosphine (PX), i.e., F, Br, Cl, CF, CN, HO, NO, and CH, and pnictide family analytes, i.e., PBr, BiI, SbI, and AsI] were predicted with intermolecular interaction energies, charge transfer (Q and Q), 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 atom) rather than the hydroxyl group (O 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 were compared.
作为手性支架在催化中的一种非共价相互作用，对金鸡纳生物碱辛可宁（）的氮族元素键合进行了模拟，以考虑这种相互作用是否具有像氢键那样控制对映面的潜力。在 中的五个反应性功能基团中，利用密度泛函理论的B3LYP/6 - 31G(d,p)水平下的分子间相互作用能、电荷转移（Q和Q）以及HOMO - LUMO的带隙能量（Eg），预测了C处的羟基（X - epi - CD1）和N处的喹啉环（X - epi - CD2）与氮族元素分析物[X = 取代膦（PX），即F、Br、Cl、CF、CN、HO、NO和CH，以及氮族元素分析物，即PBr、BiI、SbI和AsI]形成的两种稳定配合物。结果发现，表辛可宁中氮族元素键合的主要位点是喹啉环（N原子）而非羟基（O原子）。此外，在B3LYP/6 - 31 + G(d,p)水平下通过含时密度泛函理论（TD - DFT）计算了配合物的紫外 - 可见光谱，并与实验测量值进行了比较。通过这些计算，比较了 的两种分子间相互作用（氢键与氮族元素键）。
