Ab initio theoretical optical rotations of small molecules

Polavarapu, Prasad L.; Chakraborty, Dilip K.

doi:10.1016/s0301-0104(98)00381-4

Cited by 47 publications

(22 citation statements)

References 38 publications

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“…20 On the example of H 2 O 2 and H 2 S 2 , Polavarapu and Chakraborty also studied OR conformational dependence at the ab initio level. 21 Quite often, different conformers of the same molecule exhibit an opposite sign of optical rotation, e.g., as documented by Kondru et al, 22 Pecul et al, 15 Polavarapu et al, 23 and Wiberg et al 24 Apart from the conformations, several other problems complicate practical ab initio calculations of OR. The most important ones include (1) choice of suitable theoretical level (basis set, electron correlation treatment, density functional), (2) addition of the vibrational corrections, and (3) the solvent effect.…”

Section: Introductionmentioning

confidence: 99%

“…Mean average deviation (MAD) of calculated values from the experiment was $53 deg[dm(g/cm 3 )] 21 for the B3LYP functional populations. The error is higher for MP2 populations, because of the error in energy of the gg conformer of 1.…”

mentioning

confidence: 99%

“…While the DFT functionals gave values between $162 and $87 deg[dm(g/ cm 3 )] 21 , the CCSD value of $15 deg[dm(g/cm 3 )] 21 was substantially smaller. The higher OR and smaller population of gg calculated with DFT could have caused a fortuitous error cancellation and a good agreement with experiment.…”

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confidence: 99%

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Conformational behavior of simple furanosides studied by optical rotation

Kaminský¹,

Raich²,

Tomčáková³

et al. 2010

J Comput Chem

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Experimental and theoretical specific optical rotations (OR) of anhydro, epithio, and epiminoderivatives of methyl tetrofuranosides in chloroform solutions have been compared and used as a tool for exploring their conformational behavior. The potential energy surfaces of these saccharides with reduced flexibility were examined with the density functional theory and the MP2 and CCSD(T) wavefunctions methods. Theoretical ORs were obtained by Boltzmann averaging of values calculated for local minima. Resultant rotations could be used to assess the quality of the DFT and MP2 relative conformer energies. OR values calculated for equilibrium geometries in vacuum were significantly improved when the solvent was accounted for by a polarizable continuum model and first and diagonal second OR derivatives were used for an anharmonic vibrational averaging. The DFT used as a default method reproduced the experimental data fairly well. A modified B3LYP functional containing 70% of HF exchange further improved the results. Because of the strong dependence of OR on the conformation, not only the absolute configuration could be determined, but also the conformational populations were estimated. Likewise, the predicted dependence of OR on the light wavelength well agreed with experiment. The increasing precision of the contemporary computational methods thus makes it possible to relate the specific rotation to more detailed features in molecular structure.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Conformational behavior of simple furanosides studied by optical rotation

Kaminský¹,

Raich²,

Tomčáková³

et al. 2010

J Comput Chem

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“…Especially Hbonding is a difficult property to predict [68]. In the very early study of Polavarapu and Chakraborty [69] the dependence of the optical rotation of chiral 3-butyn-2-ol for different conformers was investigated. The optical rotation was highly dependent on the OH rotamer (À80.8, À30.0, and þ69.7 for the three staggered Table 12 Calculated dihedrals, populations based on free energy differences weighted by the Boltzmann equation (mpw1pw91/cc-pvdz, IEFPCM: acetonitrile), and [a] 589 values of the NH 2 eq and NH 2 ax chairs of protonated (À)-(1S,3S,4S)-neoisomenthylamine adjusted for comparison with the experimental values of the hydrochloride.…”

Section: Discussionmentioning

confidence: 99%

Stereochemical analysis of menthol and menthylamine isomers using calculated and experimental optical rotation data

Reinscheid

2016

Journal of Molecular Structure

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a b s t r a c tThe complete series of menthol isomers and their corresponding amino derivatives (base and protonated/HCl forms), were investigated using experimental and theoretical data. Our study focused on the conformational and configurational analysis, and revealed that experimental data should be used in combination with calculated data. Furthermore, even in the case of the highly studied member, menthol, discrepancies were found among previously published literature values. We show that the correct determination of the population mix is a must for the correct prediction of the absolute configuration (AC) of neoisomenthol. The neoiso forms are of special interest since a number of structural inconsistences can be found in the literature. We present a stringent proof of the AC of neoisomenthol based on literature information. To the best of our knowledge, the AC of neoisomenthylamine is for the first time shown using experimental and calculated optical rotation data. A correction of a series of publications containing an important error in the assignment of (þ)-menthylamine (correct: (þ)-neomenthylamine) is presented. With 26 data pairs (experimental versus calculated) of optical rotation values a regression is performed. The AC of all 12 compounds, even the most difficult neoiso forms, could be predicted correctly using experimental low-temperature NMR data. Furthermore, if only experimental data with an optical rotation outside the range of À10 < [a] > þ10 are used, all 12 compounds would have been correctly assigned without lowtemperature NMR data as restraints.

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“…In the beginning, most calculations were concentrated on small and rigid molecules for accuracy. Polavarapu and co-workers 4 more calculations were directed to large and flexible molecules or natural product molecules, even to the determination of the absolute configuration of molecules. 5 Moreover, the absolute configuration of more complex molecules can be determined combined with other calculations.…”

Section: Introductionmentioning

confidence: 99%

Calculations of optical rotation: Influence of molecular structure

Cao

Song

et al. 2012

J Serb Chem Soc

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Ab initio Hartree-Fock (HF) method and Density Functional Theory (DFT) were used to calculate the optical rotation of 26 chiral compounds. The effects of theory and basis sets used for calculation, solvents influence on the geometry and values of calculated optical rotation were all discussed. The polarizable continuum model, included in the calculation, did not improve the accuracy effectively, but it was superior to γs. Optical rotation of five or sixmembered of cyclic compound has been calculated and 17 pyrrolidine or piperidine derivatives which were calculated by HF and DFT methods gave acceptable predictions. The nitrogen atom affects the calculation results dramatically, and it is necessary in the molecular structure in order to get an accurate computation result. Namely, when the nitrogen atom was substituted by oxygen atom in the ring, the calculation result deteriorated

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Ab initio theoretical optical rotations of small molecules

Cited by 47 publications

References 38 publications

Conformational behavior of simple furanosides studied by optical rotation

Conformational behavior of simple furanosides studied by optical rotation

Stereochemical analysis of menthol and menthylamine isomers using calculated and experimental optical rotation data

Calculations of optical rotation: Influence of molecular structure

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