Chemoselective Divergence via Substrate Control: Decarboxylative and Decarbonylative Coupling of 2-Oxoacids with Allylic Difluorides
Bibliographic record
Abstract
Herein, we report the photocatalytic decarboxylative coupling of allylic difluorides and carbon-centered radicals, which are formed from 2-oxoacids. This mild and operationally simple protocol enables selective synthesis of monofluoroalkenes via defluorinative C–C bond formation. Primary and aryl-substituted α-ketoacids undergo direct acyl radical addition to allylic difluorides, yielding exclusively acylated products. In contrast, secondary 2-oxoacids afford mixtures of acylated and alkylated products, while tertiary 2-oxoacids selectively deliver alkylated products via a decarboxylative/decarbonylation cascade. Thus, the product distribution can be tuned by the substitution pattern on the 2-oxoacid. The rate of decarbonylation vs radical addition is based on the stability and reactivity of the radical intermediate formed. Computational studies confirm a substrate-dependent divergence in reaction pathways, with primary 2-oxoacid undergoing direct acyl radical addition, while secondary and tertiary substrates exhibit competing decarbonylation leading to alkylated products. This study therefore helps establish a mechanistic rationale for the competitive acylation/alkylation processes.
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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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 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 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".