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Record W2944303098 · doi:10.1021/jacs.9b03721

Reversible Intramolecular Cycloaddition of Phosphaalkene to an Arene Ring

2019· article· en· W2944303098 on OpenAlexaff
Liu Leo Liu, Jiliang Zhou, Levy L. Cao, Youngsuk Kim, Douglas W. Stephan

Bibliographic record

VenueJournal of the American Chemical Society · 2019
Typearticle
Languageen
FieldChemistry
TopicSynthesis and characterization of novel inorganic/organometallic compounds
Canadian institutionsUniversity of Toronto
Fundersnot available
KeywordsChemistryCycloadditionDeprotonationIntramolecular forceRing (chemistry)Bicyclic moleculeMedicinal chemistryStereochemistryDienePhotochemistryOrganic chemistryCatalysis

Abstract

fetched live from OpenAlex

The phosphepinium cation 1 is deprotonated by base generating a phosphaalkene that undergoes cycloaddition to the N-bound aromatic ring affording the 2-phosphabicyclo[2.2.2]octa-5,7-diene 2. The analogous deprotonation reaction of the less bulky phosphepinium cation 3 affords a reversible equilibrium between the phosphaalkene 4 and the corresponding cycloaddition product 5. This latter observation represents the first reversible cycloaddition of a main group multiply bonded species with an arene ring. The bicyclic species 2 was also shown to be oxidized or alkylated in reactions with S8 and MeOTf, affording 6 and 7, respectively. This finding and its implications for related cycloadditions of other main group multiply bonded species are considered computationally.

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 categoriesInsufficient 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 score0.002
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0010.000

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 head0.007
GPT teacher head0.222
Teacher spread0.214 · 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 designBench or experimental
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

Citations32
Published2019
Admission routes1
Has abstractyes

Explore more

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