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Record W4416673467 · doi:10.26434/chemrxiv-2025-6q0d0

Direct Ketone Conversion to Cyclohexynes for Alkyne-Ene Reactions

2025· article· W4416673467 on OpenAlex

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.

Bibliographic record

VenueChemRxiv · 2025
Typearticle
Language
FieldChemistry
TopicCyclization and Aryne Chemistry
Canadian institutionsUniversity of British Columbia
Fundersnot available
KeywordsCarbeneReactivity (psychology)AryneTrifluoromethanesulfonateKetoneNucleophileSilylation

Abstract

fetched live from OpenAlex

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.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

Full frame distilled prediction

Teacher imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.278
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0010.001
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.001
Science and technology studies0.0010.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0010.000
Insufficient payload (model declined to judge)0.0020.000

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.

Opus teacher head0.013
GPT teacher head0.273
Teacher spread0.261 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it