Pyrrolizidine alkaloids necine bases:Ab initio, semiempirical, and molecular mechanics approaches to molecular properties

✍ Scribed by Giordan, Marcelo; Custodio, Rog�rio; Trigo, Jos� Roberto

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 980 KB
• Volume: 17
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(19960130)17:2<156::aid-jcc3>3.0.co;2-v

✦ Synopsis

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 ' H-NMR (nuclear magnetic resonance) studies in D,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 0(11)H group and the C(l)-C(2) double bond as well as with a hydrogen bond between 0(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