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Record W2950568246 · doi:10.1002/anie.201905540

Direct Formic Acid Mediated<i>Z</i>‐Selective Reductive Coupling of Dienes and Aldehydes

2019· review· en· W2950568246 on OpenAlexafffund
Christopher Cooze, Raphael Dada, Rylan J. Lundgren

Bibliographic record

VenueAngewandte Chemie International Edition · 2019
Typereview
Languageen
FieldChemistry
TopicCatalytic C–H Functionalization Methods
Canadian institutionsUniversity of Alberta
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsChemistryElectrophileNucleophileReductive eliminationFormic acidIsomerizationOlefin fiberCatalysisTriphosAlkylDissociation (chemistry)HydroformylationLigand (biochemistry)Pincer ligandMedicinal chemistryCombinatorial chemistryPhotochemistryOrganic chemistryRhodium

Abstract

fetched live from OpenAlex

Methods for the addition of unsaturated nucleophiles to carbonyls to generate Z-olefin products remain rare and often require either alkyl borane or zinc reductants, limiting their utility. Demonstrated here is that formic acid mediates the Rh-catalyzed, Z-selective coupling of dienes and aldehydes. The process is distinguished by broad tolerance towards reducible or electrophilic groups. Kinetic analysis suggests that generation of the catalytically active Rh intermediate by ligand dissociation is the rate-determining step. The rapid generation and trapping of Rh-allyl intermediates is key to preventing chain-walking isomerization events that plague related protocols. Insights gained through this study may have wider implications in selective metal-catalyzed hydrofunctionalization reactions.

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 machine prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Not applicable · Consensus signal: none
GenreCandidate signal: Review · Consensus signal: Review
Teacher disagreement score0.002
Threshold uncertainty score0.008

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0010.001
Science and technology studies0.0000.000
Scholarly communication0.0000.001
Open science0.0000.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0020.002

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 head0.045
GPT teacher head0.336
Teacher spread0.291 · 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 source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designNot applicable
Domainnot available
GenreReview

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

Citations28
Published2019
Admission routes2
Has abstractyes

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