Palladium Catalyzed Conversion of Aryl Triflates to Acyl-DMAP Salts: A Mild and Versatile Approach to Carbonylations
Bibliographic record
Abstract
The use of metal catalysis to form potent acylating agents offers an important avenue to broaden the applicability of carbonylation reactions. However, the often disfavored reductive elimination of these reactive products presents a challenge, and has made these often high temperature, high pressure reactions and limited in their scope. Herein, we describe a mild and versatile palladium catalyzed carbonylative method to generate electrophilic acyl-DMAP (4-dimethylaminopyridine) salts by exploiting an alternative feature of these reactions: the counterion. In this, the weakly coordinating triflate anion is found to strongly destabilize Pd(II) toward irreversible reductive elimination of the reactive products, while ligand design can allow the rapid activation of aryl or vinyl triflates. Together, this provides a route to carry out palladium catalyzed carbonylations under exceptionally mild conditions, with low catalyst loading (0.5 mol % Pd), and with broadly available C(sp 2 )-triflate reagents. Coupling their formation with the addition of nucleophiles can be used to assemble a variety of products by carbonylation reactions, including those with palladium reactive functionalities.
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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) | 0.001 | 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 | 0.000 |
| 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".