Stereodynamism in Chiral Polyaromatic Phosphepines
Bibliographic record
Abstract
In the present experimental-computational study, we demonstrate that the stereodynamism of phosphahelicenoids can be used to afford diastereoisomers of chirally perturbed polyaromatics fused with a phosphepine ring (seven-membered P-cycle). The phosphahelicenoids have been synthesized through a stereospecific approach from commercially available BINAPs. In particular, using the combination of NMR, X-ray diffraction, and chiral HPLC experimental techniques with DFT and higher level ab initio calculations, we highlight a complex interplay between the inversion at the phosphorus stereocenter and the epimerization of the helicenoid framework, as well as a competition with a rearomatization reaction through P-extrusion. The impact of the conformational modifications on the structure have been studied through X-ray diffraction. The spectroscopic properties, in particular, of chiroptical nature, including circularly polarized luminescence, are also discussed in detail and compared to DFT and ADC(2) models.
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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) | 0.000 | 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) | 0.004 | 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".