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 CC bond formation. Primary and aryl 2‐oxoacids undergo direct acyl radical addition to allylic difluorides, yielding acylated products exclusively. 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 of the 2‐oxoacids. The rate of decarbonylation versus radical addition is based on the stability and reactivity of the radical intermediates formed. Computational studies confirm a substrate‐dependent divergence in reaction pathways, with primary 2‐oxoacids undergoing direct acyl radical addition, while secondary and tertiary substrates exhibit competing decarbonylation leading to alkylated products. This study therefore establishes a mechanistic rationale for competitive acylation/alkylation processes starting from 2‐oxoacids.
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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 | 0.001 |
| 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 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 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".