Mimicking Noncanonical Oxidations with Redox-Neutral Photocatalysis
Bibliographic record
Abstract
Noncanonical oxygenases are a family of Fe-containing enzymes that catalyze oxidative radical cyclizations. Despite creating key structural features that often define a natural product’s complexity, the mechanisms of these oxidations remain poorly understood and difficult to mimic. In this work, we show that noncanonical cyclizations from lignan biosynthesis can be recreated when presumed biosynthetic radicals are generated using photocatalysis. These conditions afford the ensuing electron rich radicals sufficient time to undergo challenging 5- or 11-membered ring formation that create the defining structural features of the highly oxidized lignans taiwankadsurins A, B and kadsuphilin N. By showing that these cyclizations can occur without enzymatic assistance, we provide a more general strategy for mimicking noncanonical transformations that should broaden their use in organic synthesis.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 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 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 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 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".