Ab initio DFT calculations of the configurational and conformational preferences of 2-phenylsulfinylcyclohexanones Evidence for "exo-anomeric" interactions
Bibliographic record
Abstract
The conformational analysis of 2-phenylsulfinylcyclohexanone by ab initio density functional calculations is described. Six conformations corresponding to axial/equatorial isomers and rotation about the exocyclic C2S bond in each of the RR or RS diastereomers were calculated and the results were examined in terms of relative energies, electrostatic interactions, orbital interactions, and geometrical variations. The global minimum conformation was the RS isomer that positioned the phenylsulfinyl moiety in an equatorial orientation and the sulfinyl oxygen in an anti orientation with respect to the carbonyl carbon atom. Of the other three low energy conformations, only one had a gauche arrangement of these atoms, and only in one of the four lower energy conformations was evidence found for a S-O()···C(+)-O electrostatic interaction. In contrast, the results were consistent with the operation of n S → [Formula: see text] stabilizing orbital interactions. Further support for this hypothesis was obtained from the increased C=O bond lengths in these four conformations relative to the other conformations, and by the torsional angle distortion away from ideal geometry, presumably to maximize the stabilizing orbital interaction. We propose that this conformational preference is a manifestation of a generalized exo-anomeric effect. The longer C2S bond in the axial isomers was also interpreted in terms of a stabilizing π C=O → [Formula: see text] interaction, analogous to an endo-anomeric interaction. Comparison of the computational results to available experimental data on the conformational equilibrium of each diastereomer in solution suggests which conformers are present in each of the equilibria. The available data for the solid state indicate that the RR and RS isomers both crystallize in high energy conformations, stabilized by intermolecular interactions.Key words: 2-phenylsulfinylcyclohexanones, configurational isomers, conformational preferences, DFT calculations, exo-anomeric effect.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".