N–H⋯O versus O–H⋯O: density functional calculation and first principle molecular dynamics study on a quinoline-2-carboxamide N-oxide

Jezierska, Aneta

doi:10.1007/s00894-015-2587-3

Cited by 4 publications

(3 citation statements)

References 54 publications

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“…This result strongly confirms that the hydrogenation of 4-NP over Ag-HHSPN does not occur because of the stronger hydrogen-bonding network rather than the possible aminophenol product that is not released from the catalyst. The results may be ascribed to the fact that the N–H···O bond type is appreciably weaker than the O–H···O bond …”

Section: Results and Discussionmentioning

confidence: 99%

“…Under magnetic stirring, substrates (e.g., NB and 4-NP) first access the PNIPA chain via molecule diffusion in an aqueous solution. Subsequently, the NB molecule can access the active sites (MNPs) deposited on the surface of inner-shelled SiO 2 sequentially through the PNIPA coating and SiO 2 outer layer, and then corresponding aniline is almost quantitatively released from the catalysts (Table S1) because of the appreciably weaker hydrogen bond (N–H···O), leading to the efficient hydrogenation of NB. On the contrary, 4-NP first experiences a stronger resistance from the hydrogen bond (O–H···O) between the hydroxyl group of 4-NP and secondary amino groups of the PNIPA coating.…”

Section: Results and Discussionmentioning

confidence: 99%

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Metal Nanoparticles Confined within an Inorganic–Organic Framework Enable Superior Substrate-Selective Catalysis

Yin

Xiao

et al. 2020

ACS Appl. Mater. Interfaces

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The search for catalysts with a perfect substrate selectivity toward the hydrogenation of nitroarenes is a goal of high importance, which still remains a significant challenge. Here, we designed a new type of catalyst with superior substrate selectivity by combining a space-confined effect and a hydrogen-bonding network, in which metal nanoparticles (MNPs) were confined in hierarchical hollow silica (HHS) with a poly(N-isopropylacrylamide) (PNIPA) coating. Given the strong induced properties of hydrogen-bond donors and acceptors in the HHS support and PNIPA coating, the as-synthesized catalyst would achieve perfect substrate selectivity for the hydrogenation of various nitroarenes and their mixture by thoroughly impeding the reduction of nitroarenes with any hydroxyl or carboxyl groups, which is typically very difficult to be realized over almost all of the reported supported-metal catalysts. Notably, the hydrogenation of nitroarenes can produce almost quantitative yields of anilines over the as-synthesized catalyst. Furthermore, density functional theory and experimental evidence are also provided for the hierarchical structure of HHS and PNIPA coating associated with substrates to demonstrate how a substrate could have access or be blocked into the confined active centers (MNPs). Therefore, this work would open a new window to design efficient catalysts for a wide variety of substrate-selective catalyses.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Metal Nanoparticles Confined within an Inorganic–Organic Framework Enable Superior Substrate-Selective Catalysis

Yin

Xiao

et al. 2020

ACS Appl. Mater. Interfaces

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“…In the current study, we focused on intra- and intermolecular interactions in two N -oxides: 2-(N,N-dimethylamino-N-oxymethyl)-4,6-dimethylphenyl ( 1 ) [ 43 ] and 5,5’-dibromo-3-diethylaminomethyl-2,2’-biphenol N -oxide ( 2 ) [ 44 ]. N -oxides are interesting objects for experimental and theoretical studies because of their unusual chemical structure, possessing N→O bonds, which is involved in inter- or intramolecular hydrogen bond formation [ 45 , 46 , 47 , 48 , 49 ]. It was showed that the N -oxide group exhibits proton acceptor ability for hydroxyl, carboxyl, amine groups or water molecules.…”

Section: Introductionmentioning

confidence: 99%

Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

et al. 2022

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Intra- and intermolecular interactions have been explored in selected N-oxide derivatives: 2-(N,N-dimethylamino-N-oxymethyl)-4,6-dimethylphenyl (1) and 5,5’-dibromo-3-diethylaminomethyl-2,2’-biphenol N-oxide (2). Both compounds possess intramolecular hydrogen bonding, which is classified as moderate in 1 and strong in 2, and resonance-assisted in both cases. Density Functional Theory (DFT) in its classical formulation as well as Time-Dependent extension (TD-DFT) were employed to study proton transfer phenomena. The simulations were performed in the gas phase and with implicit and explicit solvation models. The obtained structures of the studied N-oxides were compared with experimental data available. The proton reaction path was investigated using scan with an optimization method, and water molecule reorientation in the monohydrate of 1 was found upon the proton scan progress. It was found that spontaneous proton transfer phenomenon cannot occur in the electronic ground state of the compound 1. An opposite situation was noticed for the compound 2. The changes of nucleophilicity and electrophilicity upon the bridged proton migration were analyzed on the basis of Fukui functions in the case of 1. The interaction energy decomposition of dimers and microsolvation models was investigated using Symmetry-Adapted Perturbation Theory (SAPT). The simulations were performed in both phases to introduce polar environment influence on the interaction energies. The SAPT study showed rather minor role of induction in the formation of homodimers. However, it is worth noticing that the same induction term is responsible for the preference of water molecules’ interaction with N-oxide hydrogen bond acceptor atoms in the microsolvation study. The Natural Bond Orbital (NBO) analysis was performed for the complexes with water to investigate the charge flow upon the polar environment introduction. Finally, the TD-DFT was applied for isolated molecules as well as for microsolvation models showing that the presence of solvent affects excited states, especially when the N-oxide acceptor atom is microsolvated.

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Ionic Hydrogen Bond‐Assisted Catalytic Construction of Nitrogen Stereogenic Center via Formal Desymmetrization of Remote Diols

Luo,

Liao,

et al. 2024

Angewandte Chemie

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The control of noncarbon stereogenic centers is of profound importance owing to their enormous interest in bioactive compounds and chiral catalyst or ligand design for enantioselective synthesis. Despite various elegant approaches have been achieved for construction of S‐, P‐, Si‐ and B‐stereocenters over the past decades, the catalyst‐controlled strategies to govern the formation of N‐stereogenic compounds have garnered less attention. Here, we disclose the first organocatalytic approach for efficient access to a wide range of nitrogen‐stereogenic compounds through a desymmetrization approach. Intriguingly, the pro‐chiral remote diols, which are previously not well addressed with enantiocontrol, are well differentiated by potent chiral carbene‐bound acyl azolium intermediates. Preliminary studies shed insights on the critical importance of the ionic hydrogen bond (IHB) formed between the dimer aggregate of diols to afford the chiral N‐oxide products that feature a tetrahedral nitrogen as the sole stereogenic element with good yields and excellent enantioselectivities. Notably, the chiral N‐oxide products could offer an attractive strategy for chiral ligand design and discovery of potential antibacterial agrochemicals.

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N–H⋯O versus O–H⋯O: density functional calculation and first principle molecular dynamics study on a quinoline-2-carboxamide N-oxide

Cited by 4 publications

References 54 publications

Metal Nanoparticles Confined within an Inorganic–Organic Framework Enable Superior Substrate-Selective Catalysis

Metal Nanoparticles Confined within an Inorganic–Organic Framework Enable Superior Substrate-Selective Catalysis

Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

Ionic Hydrogen Bond‐Assisted Catalytic Construction of Nitrogen Stereogenic Center via Formal Desymmetrization of Remote Diols

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