Rotational spectroscopy of methyl benzoylformate and methyl mandelate: structure and internal dynamics of a model reactant and product of enantioselective reduction
Bibliographic record
Abstract
Pure rotational spectra of a prototypical prochiral ester, methyl benzoylformate (MBF), and the product of its enantioselective reduction, (R)-(-)-methyl mandelate (MM), were measured in the range of 5-16 GHz, using a cavity-based molecular beam Fourier-transform microwave spectrometer. Potential conformers were located using density functional theory calculations, and one conformer of each species was identified experimentally. The minimum energy conformer of MBF, in which the ester group is in a Z orientation, was observed for the first time. Based on an atoms-in-molecules analysis, MBF contains a weak CH···O=C hydrogen bond between the carbonyl oxygen atom of the ester group and the nearest hydrogen atom of the aromatic ring. In the minimum energy conformer of MM, the ester group is oriented to accommodate a hydrogen bond between the hydrogen atom of the hydroxyl group and the carbonyl oxygen atom (OH···O=C), rather than the sp(3) oxygen atom (OH···O-C). For both species, splittings of the rotational transitions were observed, which are attributed to methyl internal rotation, and the orientations and barrier heights of the methyl tops were determined precisely. The barrier heights for MBF and MM are 4.60(2) and 4.54(3) kJ mol(-1), respectively, which are consistent with values predicted by high-level wavefunction-based calculations. On the basis of an atoms-in-molecules analysis, we propose that destabilization of the sp(3) oxygen atom of the ester group most directly dictates the barrier height.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.000 | 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".