DFT study of the per-6-amino-β-cyclodextrin as catalyst in synthesis of 2-aryl-2,3-dihydro-4-quinolones

Abstract

The synthesis of 2-aryl-2,3-dihydro-4-quinolones in the presence of per-6-amino-β-cyclodextrin (per-6-ABCD) as catalyst can improve selectivity and yield. The interaction between per-6-ABCD and benzaldehyde or o-aminoacetophenone plays an important role in this reaction. This paper studies the complexes of per-6-ABCD with benzaldehyde and o-aminoacetophenone using density functional theory (DFT) method. The reaction process is investigated by studying the energy of the reactants and the product. Hydrogen bonds are researched on the basis of natural bonding orbital (NBO) analysis, the results propose the donor-acceptor interactions of complex. The Mulliken charge and frontier orbital are employed for revealing the charge distribution. In addition, (13)C nuclear magnetic resonance ((13)CNMR) spectroscopy shows that the carbon atom on the aldehyde group for benzaldehyde, carbonyl group and the carbon atom connected with carbonyl group for o-aminoacetophenone are apparently activated in the cavity of per-6-ABCD. The probable catalytic mechanism of per-6-ABCD is discussed in terms of the calculated parameters.

Self-Assembled Supramolecular Polyoxometalate Hybrid Architecture as a Multifunctional Oxidation Catalyst

“…The typical counterplots of HOMO and LUMO of { 3CD@SiW 12 } obtained by PBE/LANL2DZ are shown in Figure a and Figure S14. The HOMO represents the ability to donate electrons, while the LUMO as an electron acceptor represents the ability to obtain electrons . Noticeably, the HOMO and LUMO of {SiW 12 } ⊂ CD (1:1) in { 3CD@SiW 12 } are both mainly spread around the POM molecule.…”

Recent Advances in the Catalytic Synthesis of 4-Quinolones

“…In 2014, a detailed DFT method about this per-6-ABCD-catalyzed asymmetric Mannich reaction was accomplished by the Liu group. 110 Their results showed that per-6-ABCD catalyst increases the nucleophilicity of o-aminoacetophenone and the electrophilicity of benzaldehyde and donor-acceptor interactions of the complex can increase the enantioselectivity of catalytic reactions.…”