A novel synthesis of octahydropyrido[3,2- ]carbazole framework of aspidospermidine alkaloids and a combined computational, FT-IR, NMR, NBO, NLO, FMO, MEP study of the cis-4a-Ethyl-1-(2hydroxyethyl)-2,3,4,4a,5,6,7,11c-octahydro-1H-pyrido[3,2-c]carbazole

Uludag, Nesimi; Serdaroğlu, Goncagül; Yinanç, Abdullah

doi:10.1016/j.molstruc.2018.02.046

Cited by 34 publications

(11 citation statements)

References 59 publications

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“…In the past, there have been reports of the syntheses of both aspidospermidine and strychnos-type alkaloids, [14][15][16][17] but the leading role of the intermolecular or intramolecular interactions on the challenging syntheses of this group of compounds has rarely been reported by using computational tools. [18][19][20] For this reason, we decided to investigate the structure, electronic, and spectroscopic properties of demethoxyaspidospermine because the results might provide useful information for synthetic chemists. In this paper, we selected aspidospermidine as our starting material 20,21 and then performed the acylation of compound 1 with acetic anhydride in 81% of the overall yield.…”

Section: Introductionmentioning

confidence: 99%

The synthesis and spectroscopic characterization of (+)-demethoxyaspidospermine: Density functional theory calculations of the structural, electronic, and non-linear optic and spectroscopic properties

Serdaroğlu

Uludag

2019

Journal of Chemical Research

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(+)-Demethoxyaspidospermine was synthesized via the acylation of aspidospermidine with acetic anhydride, and the structure was determined by elemental analysis and Fourier-transform infrared and nuclear magnetic resonance spectroscopic tools and was supported by the simulated spectroscopic studies. Next, the stable geometries obtained by the conformational analysis performed at the B3LYP/6-31G(d, p) level were used for further investigations carried out in B3LYP and M06-2X functionals, and Hartree–Fock (HF) method, employed by the 6-311++G(d, p) basis set. Also, the natural bond orbital analysis revealed that the most contribution to the lowering of the stabilization energy came from n → π* and π → π* interactions. Moreover, the non-linear optic analysis has shown that the title compound can be a useful agent in the optoelectronic devices because of the optical properties. Also, the chemical reactivity tendency for nucleophilic or electrophilic attack reactions on the compound was evaluated by frontier molecular orbital analysis, and the reactive sites of the compound was shown by highest molecular orbital and lowest unoccupied orbital amplitudes and molecular electrostatic potential diagrams.

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Section: Introductionmentioning

confidence: 99%

The synthesis and spectroscopic characterization of (+)-demethoxyaspidospermine: Density functional theory calculations of the structural, electronic, and non-linear optic and spectroscopic properties

Serdaroğlu

Uludag

2019

Journal of Chemical Research

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“…The assignment of vibration modes that occur in the middle and low‐frequency region of the IR spectrum is a difficult task because of the mixed modes. In the literature, νCC stretching signal for the unsaturated and heterocyclic rings of a substituted carbazole compound were reported at 1620 and 1520 cm −1 , and they were calculated at the same theory level in the range of 1600–1467 cm −1 as a contaminated mode with the ipb HNC modes and 1431–809 cm −1 mixed mode with the ipb HCC modes …”

Section: Resultsmentioning

confidence: 95%

“…Addition, these alkaloids have been attracted considerable interest by synthetic chemists due to the unique challenges posed by their structural features, i. e., their pentacyclic framework, as well as their potent pharmacological properties. Therefore, the synthetic chemists commonly have looked for the new strategy to produce these natural compounds with highly efficiently . The results of a recent study of dehydroaspidospermidine indicated that the strychnos‐type indole compound could be synthesized by Fischer cyclization with a highly‐effective synthetic process, but it is quite challenging .…”

Section: Introductionmentioning

confidence: 99%

A DFT Investigation on the Structure, Spectroscopy (FT‐IR and NMR), Donor‐Acceptor Interactions and Non‐Linear Optic Properties of (±)‐1,2‐Dehydroaspidospermidine

Uludag

Serdaroğlu

2019

ChemistrySelect

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In this study, (±)‐1,2‐Dehydroaspidospermidine was analyzed by elemental analysis, 1H and 13C NMR, and FT‐IR spectra. Also, because the starting geometry is essential to evaluate the structural, electronic, and spectral properties of this compound, we used the potential energy surface (PES) scan by the B3LYP/6‐31G(d,p) hybrid functional to determine the stable structures of the (±)‐1,2‐Dehydroaspidospermidine. Thus, three stable conformations of the compound were used in all of the electronic and spectroscopic simulations performed by the M06‐2X, G96LYP, and B3LYP functionals at the 6–311++G(d,p) basis set in a vacuum and chloroform. After the observed and simulated FT‐IR and NMR data were compared, the second order perturbative theory in the NBO (Natural Bond Orbital) basis was used to interpret the critical donor‐acceptor interactions; the dominant contribution to the lowering of the second order energy for all conformers was the π→ π* and σ→ π* interactions. Also, we used both NLO (Non Linear Optic) and FMO (Frontier Molecular Orbital) analyses to investigate the non‐linear optical property and the biochemical reactivity of the compound. The results of this work demonstrated that the compound has an available non‐linear optical property (β=6.62 x 10−30 esu) that can be used in optoelectronic technology, and, besides, it has biological activity because of its strong intramolecular interactions.

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“…MEP gives an idea about the total charge density present in the molecule which is helpful to identify the molecular polarity. It also provides the information about dye interaction with another one and thereby explain the sites of electrophilicity, nucleophilic reactions . The values of the electrostatic potential at a different surface are notified by various colours, potential decreases in the order of blue> orange> red .…”

Section: Resultsmentioning

confidence: 99%

Theoretical Investigation of Optical and Nonlinear Optical (NLO) Properties of 3‐Azabenzanthrone Analogues : DFT and TD‐DFT Approach.

et al. 2019

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a] 3-Azabenzanthrone based chromophores are investigated to study the effect of different substituents on optical and "nonlinear optical (NLO)" properties by means of density functional theory (DFT) with global hybrid functionals (GHs) -B3LYP and BHandHLYP, range separated hybrid functionals (RSHs) CAMÀ B3LYP, wB97, wB97X, wB97XD and the basis sets 6-31 + G(d), cc-pVDZ, and cc-pVTZ. It is observed that the incorporation of an electron withdrawing group at the 1 position and an electron donating group at the 2 and 6 positions of 3azabenzanthrone system led to more red shifted absorption maxima and showed better NLO response. Molecule 3 with electron withdrawing -CN at the 1 position exhibited the highest absorption wavelength (λ = 590 nm). The geometries, dipole moments, HOMO-LUMO energy gaps, total hyperpolarizability are calculated to investigate the effect of different substituents on the photophysical and NLO properties of 3azabenzanthrone based chromophores. The insertion of -CN group at the 1 position of 3-azabenzanthrone system resulted in higher first order hyperpolarizability (β 0 ) .

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A novel synthesis of octahydropyrido[3,2- ]carbazole framework of aspidospermidine alkaloids and a combined computational, FT-IR, NMR, NBO, NLO, FMO, MEP study of the cis-4a-Ethyl-1-(2hydroxyethyl)-2,3,4,4a,5,6,7,11c-octahydro-1H-pyrido[3,2-c]carbazole

Cited by 34 publications

References 59 publications

The synthesis and spectroscopic characterization of (+)-demethoxyaspidospermine: Density functional theory calculations of the structural, electronic, and non-linear optic and spectroscopic properties

The synthesis and spectroscopic characterization of (+)-demethoxyaspidospermine: Density functional theory calculations of the structural, electronic, and non-linear optic and spectroscopic properties

A DFT Investigation on the Structure, Spectroscopy (FT‐IR and NMR), Donor‐Acceptor Interactions and Non‐Linear Optic Properties of (±)‐1,2‐Dehydroaspidospermidine

Theoretical Investigation of Optical and Nonlinear Optical (NLO) Properties of 3‐Azabenzanthrone Analogues : DFT and TD‐DFT Approach.

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