Synthesis of Single Isomer Trisubstituted and Tetrasubstituted Olefins from E-β-Chloro-α-Iodo-α,β-Unsaturated Esters and Bergman Cycloaromatizations With and Without a Radical Trapping Agent
Bibliographic record
Abstract
Optimized methods for the regioselective and stereospecific synthesis of both trisubstituted and tetrasubstituted olefins as single isomers from E-β-chloro-α-iodo-α,β-unsaturated esters have been developed from previous work done in the Ogilvie lab. These optimized methods have led to the synthesis of trans isomeric enediynes that can be photoisomerized to their respective cis isomers and subsequently undergo microwave-assisted Bergman cycloaromatizations. Furthermore, both cis and trans isomeric enediynes that have propargyl ether substituents have been found to be able to undergo photoactivated Bergman cyclizations without the need for an intermolecular hydrogen donor. A mechanism study has confirmed that the Bergman cyclization products that form without the presence of an intermolecular hydrogen donor undergo a series of 1,5-hydrogen shifts as intermediates. A series of optimizations to these reactions were carried out, in part by utilizing electron-donating or electron-withdrawing functional groups to help stabilize the resulting radicals that form on the intermediates, and thus increase the yield of the associated Bergman cyclization products.
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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) | 0.002 | 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".