Oxone-Mediated Radical Trifunctionalization of Allyl Carboxylates via 1,2-Ester Migration
Bibliographic record
Abstract
Radical-mediated trifunctionalization of alkenes, by enabling the rapid introduction of multiple functional groups, has emerged as one of the most effective strategies for the construction of functionally diverse and structurally complex molecules. Herein, we present a novel potassium peroxomonosulfate (Oxone)-mediated 1,2-ester migration strategy for the radical trifunctionalization of allyl carboxylates. This is the first case of achieving 1,3-hydroxyselenation or 1,3-hydroxysulfurization of allyl carboxylates via 1,2-ester migration, and Oxone served as both the oxidant and the hydroxyl source. The reaction efficiently constructs a C-Se/S bond and two C-O bonds in one step. Furthermore, combined experimental and density functional theory (DFT) calculations elucidate the reaction mechanism, revealing that the 1,2-ester migration can be realized through dual pathways, the three-membered (with an activation energy of 13.7 kcal/mol) and five-membered (with an activation energy of 14.6 kcal/mol) ring transition states.
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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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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".