Catalyst and Ring Size Effects on Periselectivity of Oxonium Ylide Rearrangements
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
Diazoketones were subjected to carbene-transfer with Rh(II) or Cu(II) catalysts to probe the selectivity for rearrangement via five- or six-membered oxonium ylides. 4,5-Bis(benzyloxy) and 4-allyloxy-5-benzyloxy substrates 3a,b showed a large preference for rearrangement via the five-membered ylide under all conditions. However, a sharp divergence was seen with 5-allyloxy-4-benzyloxy substrate 3c, which underwent predominantly a [2,3]-shift to pyran 5c via the six-membered ylide with Cu(II) catalysis and a [1,2]-shift to furan 4c via the five-membered ylide with Rh(II) catalysis.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.000 | 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 it