ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The dithionite reduction of pyridinium salts results in the preferential formation of the 1,4-dihydropyridines over the other possible (1,2 and 1,6) structural isomers. Theoretical studies performed in the framework of the AM1 molecular orbital approximation both on some simple, model molecules (dihydro-1-methyl-3-nicotinamide, 1, and dihydro-1-methyl-3-methyl-nicotinate, 2) and more complex derivatives (1-methyl-dihydro-pyridine-3-carboxylates of estradiol, 3, and azidothymidine, 4) supported thermodynamic product control. The increased relative thermodynamic stability of the 1,4-dihydropyridine isomers is explained by favorable electronic interactions (homoaromaticity, hyperconjugation) governing in these derivatives. The calculated data support existing experimental evidence for product formation and isomer stability. © 1993 John Wiley & Sons, Inc.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560480706
