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Record W1977088056 · doi:10.1139/v00-011

On the reduction of tertiary radicals by samarium diiodide (SmI<sub>2</sub>)

2000· article· en· W1977088056 on OpenAlexvenueno aff
Tadamichi Nagashima, Alexey Rivkin, Dennis P. Curran

Bibliographic record

VenueCanadian Journal of Chemistry · 2000
Typearticle
Languageen
FieldChemistry
TopicOxidative Organic Chemistry Reactions
Canadian institutionsnot available
Fundersnot available
KeywordsChemistrySamariumDeuteriumReagentRadicalIsopropylMedicinal chemistryQuenching (fluorescence)Tertiary amineSamarium diiodideDimerPhotochemistryKinetic isotope effectEtherDecompositionOrganic chemistry

Abstract

fetched live from OpenAlex

Reduction of o-iodophenyl 3-methylbut-2-enyl ether with samarium diiodide generates mixtures of 3-isopropyl-2,3-dihydrobenzofuran and 3-(2-propenyl)-2,3-dihydrobenzofuran along with a small amount of dimer. If a source of deuterium is present during the reduction, then the 3-isopropyl product predominates and this product is labeled with one deuterium. However, attempts to quench the putative tertiary organosamarium reagent by adding a deuterium source after the reduction were not very successful at room temperature. But at 0°C, the organosamarium reagent was generated (at least to the extent of about 50%, as measured by deuterium quenching), and its decomposition was followed over time by a series of quenching experiments. The results suggest that tertiary radicals are reduced to a significant extent by SmI 2 to form an anionic (presumably alkylsamarium) species. This species is thermally unstable and decomposes to the corresponding reduced and eliminated products. The reduced product is consistently formed in slight excess over the eliminated one, and the mechanism of formation of these products is not yet clear.Key words: samarium diiodide, SmI 2 , reduction, alkyl samarium.

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 score0.044
Threshold uncertainty score0.987

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 integrity0.0000.001
Insufficient payload (model declined to judge)0.0140.000

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 head0.005
GPT teacher head0.188
Teacher spread0.182 · 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

Citations10
Published2000
Admission routes1
Has abstractyes

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