Photoredox-Catalyzed Activation of C(sp3)–H Acids and Total Synthesis of Hyperolactone C
Bibliographic record
Abstract
We present a detailed study on photoredox catalysis platforms that directly engage 1,3-dicarbonyl C(sp3)–H acids towards radical reactions. This platform enables redox-neutral hydroalkylation and cross-coupling, as well as oxidative transformations that demonstrably improve on the prior state of the art. Interrogations of the underlying catalytic cycle and mechanism for this platform through kinetic, thermodynamic, and computational studies enabled the 4-step synthesis of the spirocyclic natural product hyperolactone C and unnatural analogues. The present investigations also demonstrate the key role of lithium trifluoroacetate under complementary Ce-containing and Ce-free photoredox conditions to enable ligand to metal charge transfer (LMCT) or multi-site proton coupled electron transfer (MS-PCET) activations, respectively.
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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".