Visible-Light-Mediated Aryl Ketone Coupling with Vinyl Thianthrenium Salts Enables Formal Paternò-Büchi Reaction.
Bibliographic record
Abstract
Oxetanes are valuable motifs in drug discovery, yet their synthesis from native functional groups remains challenging. The Paternò-Büchi reaction offers a direct approach by oxetane construction from alkenes and carbonyls. However, under visible- light condi-tions this platform remains limited by the high triplet energies of common carbonyls. We report a ketone-alkene coupling strategy that achieves formal Paternò-Büchi reactivity relying on the design principle of alkene radical anion formation from vinyl thi-anthrenium salts. Selective olefin reduction decouples reactivity from carbonyl redox properties, enabling the construction of 2-aryl, 2’-alkyl oxetanes that would otherwise be inaccessible by visible-light-mediated [2+2]-cycloadditions. Initial formation of β-hydroxy thianthrenium intermediates is followed by a subsequent cyclization to give 2,2’-disubstituted oxetanes under mild, visible light-enabled conditions. This approach enables a general blueprint for visible-light-mediated oxetane synthesis beyond the limitations of traditional Paternò-Büchi photochemistry.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.002 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.003 |
| 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; both teacher heads agree on what is shown here.
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".