Synthetic Studies in the Intramolecular Carbocyclization of <i>N</i>-Acyloxyiminium Ions. Stereoelectronic and Steric Implications of Nucleophilic Alkene, Alkyne, and Allene Tethers
Bibliographic record
Abstract
N-Acyloxyiminium ions generated from 4-substituted l-pyroglutamic esters with 4-(3-butenyl), 4-(3-butynyl), 4-(3-cinnamylmethyl), and 4-allenic tethers undergo rapid Lewis acid mediated carbocyclization to give stereodefined azacyclic compounds depending on the nature of the nucleophilic tether. In general, reactions of alkenes and alkynes with terminal alkyl or aryl substituents, as well as allenes, proceed through transient vinylic carbocations that are attacked internally by the N-Boc group to give tricyclic dihydrooxazinones. Diastereotopic bis-4-(3-butenyl) and 4-(3-butynyl) tethers undergo stereochemically controlled attack favoring an antiperiplanar rather than synclinal approach to give enantiopure 6-halo octahydroindole-2-carboxylic acids and 6-halo hexahydroindole-2-carboxylic acids as their methyl esters, respectively. The aza bicyclic and tricyclic compounds are excellent scaffolds for diversification.
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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 | 0.001 | 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".