Ab initio investigation of conformation-transmission effects in 4,4-dimethylandrostan-3-one

by Ramek, M.; Kelterer, A. M.; Newton, S. Q.; vanAlsenoy, C.; Schafer, L.

The chair-boat interconversion of 2,2,4-trimethylcyclohexanone (TMC) has been studied by 4-21G ab initio calculations of the isolated compound, and of the compound as the A-ring in the larger systems 1,5,5-trimethylbicyclo[4.4.0]decan-4-one (TMD) and 4,3-dimethylandrostan-3-one (DMA). The chair-boat energy differences are 11.2, 5.9, and 3.2 kJ mol(-1) for TMC, TMD, and DMA, respectively, indicating conformation-transmission effects on the A ring by factors which originate from the C- and D-rings of the steroid. The results are compared to those of empirical methods with various force fields.

Journal
Journal of Molecular Structure-Theochem
Volume
389
Issue
3
Year
1997
Start Page
241-250
URL
https://dx.doi.org/10.1016/s0166-1280(96)04744-6
ISBN/ISSN
0166-1280
DOI
10.1016/s0166-1280(96)04744-6