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Record W4306381981 · doi:10.26434/chemrxiv-2022-zhvtf

Is Schleyer’s Predicted All-Cis [10]Annulene an Unstable Framework?

2022· preprint· en· W4306381981 on OpenAlexafffund
Karnjit Parmar, Christa S. Blaquiere, Brianna Lukan, Sydnie Gengler, Michel Gravel

Bibliographic record

VenueChemRxiv · 2022
Typepreprint
Languageen
FieldChemistry
TopicSynthesis and Properties of Aromatic Compounds
Canadian institutionsUniversity of Saskatchewan
FundersNatural Sciences and Engineering Research Council of CanadaDeutscher Akademischer AustauschdienstCompute Canada
KeywordsAnnuleneAromaticityCyclopropaneDegenerate energy levelsChemistryRing strainStereochemistryRing (chemistry)Computational chemistryCrystallographyMoleculePhysicsOrganic chemistryQuantum mechanics

Abstract

fetched live from OpenAlex

In this work we describe the synthesis of a long sought after planar [10]annulene. Remarkably, the efforts also led us to discover a completely unexpected and highly aromatic cyclopropa mono-trans[10]annulene. The parent [10]annulene (cyclodecapentaene) is non-planar and thus non-aromatic because the aromatic stabilization energy is not sufficient to overcome the strain involved in expanding CCC bond angles from the standard 120° to the necessary 144°. Interestingly, it was theorized by Schleyer (10.1021/ja953126i) that planar structures could be attained by adding cyclopropane (or cyclobutane) rings to the periphery. We opted to target the dicyclopropa[10]annulene derivative that was proposed as it was a formal cyclopropanation of our previously found stable dehydrocyclopropa[10]annulene (10.1038/s44160-022-00135-z, 10.26434/chemrxiv.14458653.v1). It was also presumed that the symmetry present within the structure would make the Kekulé structures degenerate, thus improving aromaticity substantially. However, we were uncertain if the structure would be kinetically stable and wished to attempt a synthesis to investigate it further. In this paper we describe our evolving synthetic strategy that ultimately led us to the preparation of the dicyclopropa[10]annulene. Interestingly we noted that the framework itself was rather unstable and degraded quite rapidly. We also observed that the final preparation of the desired material led to a significant side product that was identified as a cyclopropa mono-trans[10]annulene. This side product was completely unexpected and found to be more kinetically persistent than the original target.

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.

How this classification was reachedexpand

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)0.000
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: Not applicable · Consensus signal: Not applicable
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.186
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0010.001
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0020.002
Research integrity0.0010.002
Insufficient payload (model declined to judge)0.1860.000

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 head0.054
GPT teacher head0.287
Teacher spread0.233 · 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

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

Study designNot applicable
Domainnot available
GenreEmpirical

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".

Quick stats

Citations0
Published2022
Admission routes2
Has abstractyes

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