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Pyrrolizidine alkaloids necine bases: Ab initio , semiempirical, and molecular mechanics approaches to molecular properties
Author(s) -
Giordan Marcelo,
Custodio Rogério,
Trigo José Roberto
Publication year - 1996
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(19960130)17:2<156::aid-jcc3>3.0.co;2-v
Subject(s) - mndo , chemistry , ab initio , pseudopotential , computational chemistry , conformational isomerism , ab initio quantum chemistry methods , molecule , crystallography , atomic physics , organic chemistry , physics
The structural stabilities of endo and exo conformations of retronecine and heliotridine molecules were analyzed using different ab initio , semiempirical, and molecular mechanics methods. All electron and pseudopotential ab initio calculations at the Hartree‐Fock level of theory with 6‐31G* and CEP‐31G* basis sets provided structures in excellent agreement with available experimental results obtained from X‐ray crystal structure and 1 H‐NMR (nuclear magnetic resonance) studies in D 2 O solutions. The exo conformations showed a greater stability for both molecules. The most significant difference between the calculations was found in the ring planarity of heliotridine, whose distortion was associated with the interaction between the O(11)H group and the C(1)‐C(2) double bond as well as with a hydrogen bond between O(11)H and N(4). The discrepancy between pseudopotential and all‐electron optimized geometries was reduced after inclusion of the innermost electrons of C(1), C(2), and N(4) in the core potential calculation. The MNDO, AM1, and PM3 semiempirical results showed poor agreement with experimental data. The five‐membered rings were observed to be planar for AM1 and MNDO calculations. The PM3 calculations for exo ‐retronecine showed a greater stability than the endo conformer, in agreement with ab initio results. A good agreement was observed between MM3 and ab initio geometries, with small differences probably due to hydrogen bonds. While exo ‐retronecine was calculated to be more stable than the endo conformer, the MM3 calculations suggested that endo ‐heliotridine was slightly more stable than the exo form. © 1996 by John Wiley & Sons, Inc.