A DFT investigation into the origin of regioselectivity in palladium-catalyzed allylic amination
Bibliographic record
Abstract
The addition of amines or aziridines to prenylacetate is catalyzed by palladium phosphine complexes. The first-formed products have recently been shown to be the branched olefins R2NCMe2CH=CH2, R = alkyl, or R2 = 1,2-C6H10, for example. DFT calculations using the MPW1K functional were performed on reactions of the suspected intermediate η3-prenyl complex [Pd(η3-Me2CCHCH2)(PH3)2]+ with dimethylamine and ethylene imine. The activation barrier for the nucleophilic attack by the amine or the aziridine is calculated to be similar for either the sterically hindered site of the π-allyl ligand to produce the branched olefin complex or the unhindered site to give the linear olefin complex. Therefore, these calculations do not reveal the experimentally observed preference for attack. This observation, along with the experimental observation of lack of isomerization of the branched olefin product of the aziridine reactions, appears to rule out the intermediacy of a π-allyl complex [Pd(η3-Me2CCHCH2)L2]+, L = phosphine or L2 = diphosphine in the C–N bond-forming reaction.Key words: allyl palladium, amine, aziridine, DFT, mechanism, catalysis.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.000 |
| Insufficient payload (model declined to judge) | 0.005 | 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".