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Record W2949539191 · doi:10.1021/jo802728u

Oxidative Friedel−Crafts Reaction and its Application to the Total Syntheses of <i>Amaryllidaceae</i> Alkaloids

2009· article· en· W2949539191 on OpenAlex
Kimiaka C. Guérard, Cyrille Sabot, Léanne Racicot, Sylvain Canesi

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.
fundA Canadian funder is recorded on the work.

Bibliographic record

VenueThe Journal of Organic Chemistry · 2009
Typearticle
Languageen
FieldChemistry
TopicOxidative Organic Chemistry Reactions
Canadian institutionsUniversité du Québec à Montréal
FundersNatural Sciences and Engineering Research Council of CanadaAmerican Chemical Society Petroleum Research Fund
KeywordsAmaryllidaceae AlkaloidsChemistryHypervalent moleculeUmpolungRing (chemistry)Total synthesisFriedel–Crafts reactionRegioselectivityOrganic chemistryReagentStereochemistryCombinatorial chemistryNucleophileAlkaloidCatalysis

Abstract

fetched live from OpenAlex

An oxidative Friedel-Crafts reaction involving different aromatic compounds mediated by a hypervalent iodine reagent has been performed, using polysubstituted phenols. The strategy fits within the concept of "aromatic ring umpolung", which opens up novel opportunities in chemical synthesis. The reaction takes place in useful yields, and allows rapid access to highly functionalized compounds containing a dienone, a quaternary carbon center, and an aromatic ring. The product's skeleton is present in numerous natural products. As an illustration of the potential of this transformation, total syntheses of compounds belonging to the Amaryllidaceae alkaloids family such as O-methyljoubertiamine, mesembrine, and its natural derivative the dihydro-O-methylsceletenone have been achieved in eight/nine steps. The synthetic route to these molecules features a novel and efficient transformation on the basis of a Fukuyama and Michael-retro-Michael tandem process to produce the required nitrogen-containing ring system.

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)0.000
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 score0.009
Threshold uncertainty score0.716

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
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 integrity0.0000.001
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 head0.009
GPT teacher head0.232
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