The role of molecular geometry in the Wolff rearrangement of α-diazocarbonyl compounds Conformational control or structural constraints?
Bibliographic record
Abstract
Relaxed scans of potential energy surfaces for the loss of nitrogen from four different diazocarbonyl compounds: 3-diazo-2-butanone (1), 2-diazocyclohexanone (2), methyl diazomalonate (3), and diazo Meldrum's acid (4), were conducted at the B3LYP/6-31+G(d,p) level. The geometries of species and transition states involved in the process were optimized at the B3LYP/6-311+G(3df,2p) level, while electronic energies were computed using the MP2(full)/aug-cc-pVTZ method. These calculations suggest that the rigidity of cyclic molecules, rather than the conformational structure of the starting diazocarbonyl compounds, defines the pathway of the dediazotization reaction. In acyclic diazocarbonyl compounds, loss of nitrogen results in the formation of a carbene, which is stabilized by the overlap of the system of carbonyl group and the unshared electron pair of a singlet carbene. On the contrary, in small- to medium-sized cyclic systems, carbonyl carbenes are unable to attain a stabilizing orthogonal conformation. Consequently, cyclic carbonyl carbenes are less stable, and the concerted Wolff rearrangement becomes the predominant process. Transition states for the concerted Wolff rearrangement and for the formation of carbonyl carbenes have a very similar geometry.Key words: diazocarbonyl compounds, Wolff rearrangement, conformation, carbene, ketene.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 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".