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 machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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 source (direct Gemma or distilled Codex), 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".