NHCs and Visible Light-mediated Photoredox Co-catalyzed Radical 1,2-Dicarbonylation of Alkenes for 1,4-Diketones
Bibliographic record
Abstract
Alkenes are ubiquitous, and radical difunctionalization of alkenes represents one of the most practical approaches to constructing value-added compounds. Dicarbonylation of alkenes provides direct access to value-added 1,4-dicarbonyl compounds. However, selectivity control for unsymmetric 1,2-dicarbonylation is an unclosed challenge. We herein describe NHCs and photocatalysis co-catalyzed three competent radical 1,2-dicarbonylation of alkenes by distinguishing two carbonyl groups, providing structurally diversified 1,4-diketones. Mechanistic studies indicated that NHCs-stabilized ketyl-type radicals originate from aroyl fluorides via oxidative quenching process of excited photocatalysis, and acyl radicals are generated from single-electron-oxidation of α-keto acids. Distinct properties of acyl radical and NHCs-stabilized ketyl radical contributed to selectivity control. Transient acyl radicals are rapidly added to alkenes delivering alkyl radicals, which undergo subsequent radical-radical cross-coupling with ketyl-type radicals, affording 1,2-dicarbonylation products. This transformation features mild reaction conditions, broad substruct scope, and excellent selectivity, providing a general and practical approach for the dicarbonylation of olefins.
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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 | 0.000 |
| 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 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".