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Record W2333258192 · doi:10.1021/cs500539m

Operation of the Boomerang Mechanism in Olefin Metathesis Reactions Promoted by the Second-Generation Hoveyda Catalyst

2014· article· en· W2333258192 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

VenueACS Catalysis · 2014
Typearticle
Languageen
FieldChemistry
TopicSynthetic Organic Chemistry Methods
Canadian institutionsUniversity of Ottawa
Fundersnot available
KeywordsMetathesisCatalysisRing-opening metathesis polymerisationChemistryAcyclic diene metathesisSalt metathesis reactionCombinatorial chemistryOrganic chemistryPolymerization

Abstract

fetched live from OpenAlex

A long-standing question in olefin metathesis centers on whether the “release–return” (boomerang) mechanism contributes to the productivity of Hoveyda-class catalysts. According to this mechanism, a molecule of o -isopropoxystyrene ( A ) is liberated during catalyst initiation, but recaptures the active catalyst following metathesis. The relevance of this pathway for the second-generation Hoveyda catalyst HII was assessed in metathesis of 1,1- and 1,2-disubstituted olefins. Crossover studies with 13 C-labeled A *, as well as competition experiments involving ring-closing or cross metathesis (RCM, CM) in the presence of A (equimolar with HII ) indicated rapid reuptake of styrenyl ether. The crossover studies indicated highly efficient catalyst initiation, with the entire catalyst charge being activated before metathesis was complete. In a comparative study involving CM of anethole with methyl acrylate, sustained activity was shown for HII, whereas the second-generation Grubbs catalyst GII was rapidly deactivated. These data demonstrate that the release–return mechanism is indeed operative for HII in these demanding metathesis reactions, and that facile shuttling from a protected recapture cycle into the productive metathesis cycle contributes to the superior performance of HII relative to GII .

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)0.001
metaresearch head score (Gemma)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
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 score0.003
Threshold uncertainty score0.890

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.001
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 head0.015
GPT teacher head0.238
Teacher spread0.223 · 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