Geometry and energy of amidoenethiolate conformers formed by ring-opening of several thiazolium ions in base: a theoretical study using density functional theory
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Bibliographic record
Abstract
An interesting aspect of the ring-opening of thiamine and certain other thiazolium ions is the biphasic kinetics of the ring reclosure process. It has previously been proposed that the two amide rotamers of the ring-opened amidoenethiolates are responsible for the two kinetic processes. We have carried out Hartree-Fock and density functional theory calculations on a series of amidoenethiolates and their corresponding tetrahedral intermediates. The corrected gas phase energy difference of 14.6 kJ/mol between 1c and 2c supports the notion that the two rotamers can exist in solution in sufficient quantities to give rise to two kinetic processes. The major enethiolate conformer should cyclize more rapidly (after protonation) than the minor conformer in agreement with previous observations. The most stable tetrahedral intermediate has a geometry that suggests stabilization by the anomeric effect.
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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) | 0.000 | 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 it