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Record W2600952142 · doi:10.1139/cjc-2016-0574

Mechanistic insights into the Ag(I)-catalyzed aryl migration

2017· article· en· W2600952142 on OpenAlexvenueno aff
Xiang Zhang

Bibliographic record

VenueCanadian Journal of Chemistry · 2017
Typearticle
Languageen
FieldChemistry
TopicCatalytic C–H Functionalization Methods
Canadian institutionsnot available
Fundersnot available
KeywordsDeprotonationChemistryArylCatalysisDensity functional theoryMedicinal chemistryRadical ionReaction mechanismCatalytic cyclePhotochemistryAryl radicalComputational chemistryOrganic chemistryIon

Abstract

fetched live from OpenAlex

Theoretical investigation has been conducted into the mechanism for the Ag(I)/PhI(OTFA) 2 -catalyzed 1,4-radical aryl migration from carbon center to nitrogen center in sulfonamides by using density functional theory (DFT). The calculations show that 11 elementary reactions compose the whole catalytic reaction, which includes the deprotonation, the oxidation of Ag(I) intermediate to Ag(II) intermediate, the formation of nitrogen radical, the 1,4-radical aryl migration, the oxidation of benzyl radical to benzyl cation, etc. The difference between sulfonamides and other amides in the deprotonation process accounts for the experimental phenomenon that only the sulfonamides perform the deprotonation and subsequent 1,4-radical aryl migrations. Moreover, migrations of this kind proceed via a five-membered spirocyclic radical intermediate and favor the electron-rich phenyl group.

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)0.002
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 score0.114
Threshold uncertainty score0.998

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.002
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0010.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0030.000

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 head0.019
GPT teacher head0.256
Teacher spread0.238 · 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

Citations4
Published2017
Admission routes1
Has abstractyes

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