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Record W3206401536 · doi:10.26434/chemrxiv.13669235.v1

Origin of Protonation Side Products in Pd-Catalyzed Decarboxylative Allylation Reactions: Evidence for In Situ Modification of Triphenylphosphine Ligand

2021· preprint· en· W3206401536 on OpenAlexafffund
Monica A. Gill, Samuel W. J. Shields, Jeff Manthorpe

Bibliographic record

VenueChemRxiv · 2021
Typepreprint
Languageen
FieldChemistry
TopicCatalytic C–H Functionalization Methods
Canadian institutionsCarleton University
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsProtonationChemistryLigand (biochemistry)TriphenylphosphineCatalysisPalladiumCombinatorial chemistryOrganic chemistry

Abstract

fetched live from OpenAlex

Palladium-catalyzed decarboxylative allylation (DcA) is a well-established method of carbon-carbon bond formation. This type of coupling is quite attractive, as the only byproduct is CO2. While a wide variety of ligands have been employed with Pd(0) or Pd(II) precatalysts in DcA reactions, the ligand structure is most often based on a triarylphosphine core. Despite their demonstrated utility, DcA processes have been hindered by the formation of protonation side products. While this phenomenon has been widely acknowledged, little has been reported on the origin of the proton. Herein, we address this and provide multiple lines of experimental evidence for the proton originating from the triarylphosphine ligand.

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)0.001
metaresearch head score (Gemma)0.009
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMetaresearch, Meta-epidemiology (narrow)
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 score0.008
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.009
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.001
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

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 head0.119
GPT teacher head0.369
Teacher spread0.251 · 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

Citations0
Published2021
Admission routes2
Has abstractyes

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