Direct Ketone Conversion to Cyclohexynes for Alkyne-Ene Reactions
Bibliographic record
Abstract
Cyclohexynes are highly strained intermediates that are largely underexplored compared to benzynes as their aromatic counterparts. Previous strategies towards generating cyclohexynes include accessing precursors with specific functionality such as silyl vinyl triflates, vinyl halides, vinyl pseudohalides, diazirines, carbene precursors, or diacyl peroxides among others. Ultimately, the stepwise buildup of these starting materials and the transient nature of cyclohexynes has led to their synthetic utility being limited to specific classes of reactions including cycloadditions and nucleophilic trapping. To address these challenges, we envisioned accessing cyclohexynes directly from ketones, one of the most abundant and easy to install functional groups. In this work, we report forming cyclohexynes from ketones via a vinyl triflate intermediate formed in situ. These cyclohexynes then undergo a cyclohexyne-ene reaction, an unprecedented mode of reactivity for this strained intermediate. The work presented herein highlights an alternative strategy towards generating cyclohexynes and expands their synthetic utility.
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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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.005 | 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".