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Record W4294091283 · doi:10.1139/cjc-2022-0151

Regioselectivity in Wacker oxidations of internal alkenes: antiperiplanar effects?

2022· article· en· W4294091283 on OpenAlexaffvenue
W.O. Usama, Daniel J. Markewich, Allan L. L. East

Bibliographic record

VenueCanadian Journal of Chemistry · 2022
Typearticle
Languageen
FieldChemistry
TopicOxidative Organic Chemistry Reactions
Canadian institutionsUniversity of ReginaUniversity of SaskatchewanMcMaster University
Fundersnot available
KeywordsChemistryRegioselectivityChelationAlkane stereochemistryRing (chemistry)Wacker processStereochemistryOrganic chemistryMoleculePalladiumCatalysis

Abstract

fetched live from OpenAlex

Computational chemistry, with considerable effort, was used to elucidate the reason for regioselectivity (12:1 distal:proximal product distribution) in a published Wacker oxidation of internal alkenes with a homoallylic lactam ring. Such a distribution is reproduced by a non-chelating reaction pathway; chelated intermediates are found to be too high in energy. Despite much speculation of chelation effects in the literature, this particular result is most probably an antiperiplanar field effect with no chelation. Partial charge data are provided to support the proposed antiperiplanar effect. The great care needed in modelling Wacker oxidations is emphasized, but optimism is offered that its various product mysteries can be elucidated on a case-by-case basis.

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 score0.032
Threshold uncertainty score0.995

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)0.0050.000

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 head0.007
GPT teacher head0.207
Teacher spread0.201 · 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

Citations1
Published2022
Admission routes2
Has abstractyes

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