Global conformational analysis and the anomeric interactions of methanediol, methanediamine and aminomethanol

Chang, Ying-Pin; Su, Tingwei

doi:10.1016/0166-1280(96)04488-0

Cited by 28 publications

(49 citation statements)

References 37 publications

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“…The agreement observed between the MP2/6-31G * * //HF/ 6-31G * * and MP2/6-31G * * //MP2/6-31G * * results also indicates that the influence of geometrical correlated optimization on the relative energies is probably negligible for the compounds studied. Moreover, the relative energies for 1 at the MP2/ 6-311+G(2d,p)//MP2/6-31G(2d,p) level 7 are in good agreement with our HF/6-31G * * //HF/6-31G * * results. These features suggest that, for the compounds studied here, the quality of the HF/6-31G * * calculations can be considered adequate for a further analysis of the origin of the anomeric effect, and will be taken as the reference for now on.…”

Section: Nssupporting

confidence: 87%

“…This conclusion agrees with that proposed by Chang et al, employing a different energy decomposition scheme. 7 The comparison between methylenediamine, aminomethanol, and methanediol, with units N-C-N, N-C-O, and O-C-O, respectively, showed that the successive replacement of N by O increases the stability of the favored conformers. This fact is related to the reduction of repulsions between parallel bonds in the conformers with favored anomeric orientations.…”

Section: Discussionmentioning

confidence: 99%

“…An analogous conclusion was achieved employing a different method from NBO. 7 The influence on the anomeric effect of successive replacements of N by O could be analyzed comparing methylenediamine (H 2 N-CH 2 -NH 2 , 1), aminomethanol (HO-CH 2 -NH 2 , 12), 11e and methanediol, (HO-CH 2 -OH, 13). 11a The results obtained from the NBO analysis of the HF/6-31G * * wave functions of these compounds are shown in Table III.…”

Section: Methylenediamine (1)mentioning

confidence: 99%

“…To this end, we performed ab initio MO calculations and NBO analyses on substances shown on Scheme 1: methylenediamine (1), N-methyl-methylenediamine (2), 1,1-ethylenediamine (3), N, N-dimethyl-methylenediamine (4), N-methyl-1,1-ethylenediamine (5), N,N -dimethylmethylenediamine (6), N, N (SR)-dimethyl-methylenediamine (7), N, N-dimethyl-1,1-ethylenediamine (8), N,N,N -trimethyl-methylenediamine (9), N, N -dimethyl-1, 1-ethylenediamine (10), and N, N, N , N -tetramethyl-methylenediamine (11). The only experimental information available for these compounds is an electron diffraction study of 11.…”

mentioning

confidence: 99%

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Role of the anomeric effect in methanediamines in the gas phase and aqueous solutions

Carballeira¹,

Prez-Juste²

2000

J. Comput. Chem.

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An ab initio study of methylenediamine and several methylated derivatives in the gas phase and aqueous solution was performed. The conformational preferences can be considered adequately described at the HF/6-31G * * //HF/6-31G * * level, because these results agree with those obtained using larger basis sets and including ZPE and electron correlation. The energy ordering is clearly dependent on the number and position of the methyl groups present in a molecule. For a first set of the compounds, the energies obtained were interpreted in terms of the anomeric effect because the favored conformers show two or one anti orientation between the nitrogen lone pair and the C-N polar bond. Reverse anomeric effects were found for a second set of compounds. The NBO analysis was used to interpret these energetic tendencies and the rotational barrier around the N-C bonds. Thus, the preference for the anti-Lp-N-C-N orientations is mainly due to charge delocalization, always stronger than the electrostatic and steric contributions included in the Lewis term. However, the origin for the reverse anomeric effect may be related to the steric hindrance associated with the methylation. The influence of water on the conformational preferences was evaluated by means of the PCM method. Contrary to expectation, the anomeric effect is not reduced in water, and the most stable conformers in the gas phase are maintained in solution. The electrostatic term of the free solvation energy is the main responsible of the energetic changes, and depends strongly on local solute-solvent interactions.

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Section: Nssupporting

confidence: 87%

Section: Discussionmentioning

confidence: 99%

Section: Methylenediamine (1)mentioning

confidence: 99%

mentioning

confidence: 99%

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Role of the anomeric effect in methanediamines in the gas phase and aqueous solutions

Carballeira¹,

Prez-Juste²

2000

J. Comput. Chem.

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“…In other molecules that exhibit gauche effect, the orbital interaction origin of the gauche effect has been explored with the natural bond orbital (NBO) analysis, 37b, 38 and the electrostatic origin of the gauche effect has been analyzed on the basis of dipole-dipole, dipole-quadrupole, and quadrupole-quadrupole interactions. 39 Similar analyses may be applied to elucidate the origin of the gauche effect exhibited by MDP.…”

Section: Mdp Methyl Conformation: Sp3 C-h O Hydrogen Bond and Gaumentioning

confidence: 96%

Conformational analysis of three pyrophosphate model species: Diphosphate, methyl diphosphate, and triphosphate

et al. 1999

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Whereas theoretical investigations of the energetic origin of hydrolyzing a pyrophosphate linkage abound, few studies have focused on the energetics of the rotation of this linkage. This less‐studied property of the pyrophosphate linkage was investigated here by use of ab initio calculations to characterize the conformational space of three model species of pyrophosphate anions: diphosphate (P2O 7−4), methyl diphosphate (CH3P2O 7−3), and triphosphate (P3O 10−5). By carefully selecting conformationally distinct rotational isomers of the three model compounds, their potential surfaces were thoroughly explored. In addition to showing that a terminal phosphate group is indeed very flexible in accordance with the general perception of free rotation, a number of intriguing features of this linkage emerged from the ab initio calculations, which include an influential sp3‐hybridized CHO intramolecular hydrogen bond in methyl diphosphate, and a highly restricted rotational space pertaining to the central pyrophosphate linkage of the triphosphate anion. These ab initio findings were then evaluated by, and proved insightful in, follow‐up examinations of experimentally determined complex structures of proteins and their dinucleotide or adenine and guanine triphosphate ligands. © 1999 John Wiley & Sons, Inc. J Comput Chem 20: 1702–1715, 1999

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Anab initio interpretation in gas phase and aqueous solution of the generalized anomeric effect in R?O?CR2?NR2 (R = H, CH3)

Carballeira

Prez-Juste

2000

J. Comput. Chem.

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Global conformational analysis and the anomeric interactions of methanediol, methanediamine and aminomethanol

Cited by 28 publications

References 37 publications

Role of the anomeric effect in methanediamines in the gas phase and aqueous solutions

Role of the anomeric effect in methanediamines in the gas phase and aqueous solutions

Conformational analysis of three pyrophosphate model species: Diphosphate, methyl diphosphate, and triphosphate

Anab initio interpretation in gas phase and aqueous solution of the generalized anomeric effect in R?O?CR2?NR2 (R = H, CH3)

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