Ring-chain equilibria of R-but-3-enoate esters — A quantum mechanical study of direct and indirect ring-closing reactions
Bibliographic record
Abstract
Macrocyclic structures can be synthesized through two simultaneous olefin metathesis reactions: either directly through ring-closing metathesis (RCM) or indirectly through an intermediate formed by acyclic diene metathesis (ADMET). The proclivity of a homologous series of 16 R-but-3-enoate esters to form lactones through one of these two processes is studied at the HF/6–31G(d), B3LYP/6–31G(d), and MP2(full)/6–31G(d) levels of theory. Computed Gibbs free energies are used to determine ΔG RCM , ΔG ADMET , and ΔΔG (ΔG RCM – ΔG ADMET ). ΔΔG is evaluated to compare the relative favourability of the RCM and ADMET reactions for the various R-but-3-enoate esters, where each system is differentiated by the number of methylene groups (n) added to the ester chain. When n = 0, 1, 10, or 13, cyclic lactone formation by direct RCM is predicted to be thermodynamically favoured, and the indirect synthesis is preferred for all other heterocyclic structures. The same trend holds between 298.15 and 333.15 K, therefore, the gas-phase model is a reasonable approximation of the experimental reaction conditions. The theoretical model is sufficient for smaller systems, but molecules larger than the n = 6 case do not follow experimental results for similar saturated structures. Hence, the assumptions pertaining to straight-chain and cis-ring conformations need to be re-evaluated. In particular, chain flexibility should be further examined.
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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 | 0.001 | 0.002 |
| 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".