Development of Palladium-Catalyzed Decarboxylative Allylation of Electron-Deficient Sulfones: Method Development and Mechanistic Studies
Bibliographic record
Abstract
Palladium-catalyzed decarboxylative allylation is a powerful method of carbon-carbon bond construction. This methodology relies on an electron-withdrawing group to promote the reaction. The use of sulfones in decarboxylative allylation has been explored using both the trifluoromethylsulfonyl (triflyl) group, as well as the bis(3,5-trifluoromethyl)phenylsulfonyl (BTMP) group. These substrates are highly reactive at room temperature (triflyl) and 50 oC (BTMP sulfones). A detailed mechanistic study using deuterium-labelled substrates was performed to understand the origin of the protonation side-product. It was proposed that a β-hydride elimination from the η1 allyl on palladium could generate a palladium hydride intermediate along with an allene. Although small amounts of deuterium incorporation were observed in the protonated products, the proposed mechanism could not be the major pathway. Using isotopically labelled ligand, however, all protonation was surpressed. This suggests that the origin of the proton is actually from the ligand and that kinetic isotope effects may be responsible for inhibiting the protonation pathway with labelled ligand.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 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".