Controlling the regioselectivity of the di-π-methane rearrangements of 1,2-naphtho-annelated barrelene derivatives — Solution versus solid-state photochemistry
Bibliographic record
Abstract
The synthesis of 1,2-naphtho-annelated barrelene derivatives, namely dimethyl-7,12-dihydro-7,12-ethenobenzo[a]anthracene-13,14-dicarboxylate (4a) and dimethyl-7,14-dihydro-7,14-ethenodibenzo[a,j]-anthracene-15,16-dicarboxylate (4b), and the investigation of their photoreactivity in solution and in the solid state is reported. The irradiation of 4a and 4b resulted in regioselective di-π-methane rearrangements to give semibullvalene products; however, the product distribution is inverted upon changing the reaction medium from solution to the solid state. In solution, an α-naphtho–vinyl bridging predominates as the initial photochemical step because of the selective stabilization of the corresponding transition state, as discussed on the basis of the structures of the related biradical intermediates, whereas the solid-state photoreaction is significantly influenced by the steric constraints within the crystal lattice that only allow a β-naphtho–vinyl bridging.
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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) | 0.001 | 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".