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 R 2 NCMe 2 CH=CH 2 , R = alkyl, or R 2 = 1,2-C 6 H 10 , for example. DFT calculations using the MPW1K functional were performed on reactions of the suspected intermediate η 3 -prenyl complex [Pd(η 3 -Me 2 CCHCH 2 )(PH 3 ) 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(η 3 -Me 2 CCHCH 2 )L 2 ] + , L = phosphine or L 2 = 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 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 | 0.000 |
| 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 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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".