Development of enantioselective intramolecular N-arylation reactions for the desymmetrization of achiral dinitrogen malonamide derivatives
Bibliographic record
Abstract
An effective methodology for the enantioselective intramolecular (Buchwald-Hartwig) amidation of prochiral dinitrogen malonamide derivatives has been developed in quantitative yield and good enantioselectivities. The best result was obtained based on an enantiopure (R)-MOP/Pd(OAc)₂ catalytst system with either Cs₂CO₃ or K₃PO₄ in refluxing THF affording the 4-methoxybenzyl substituted diamide derivative, 3-methyl-N, 1-bis(4-methoxbenzyl)-2-oxo-1,2,3,4-tetrahydroquinoline-3-carboxamide, in 99% yield and 75% enantiomeric excess. This example serves as a preliminary example of a desymmetrization of prochiral dinitrogen nucleophiles by preferential N-arylation. The intermolecular version of this reaction proved to be more challenging than its intramolecular counterpart and no coupling products were obtained. Other malonamide derivatives were prepared with a pendant bromovinyl substituent at the αposition and cyclized intramoleculary employing a mild Goldberg reaction to form 5-membered rings in good yield and unknown enantioselectivity.
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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".