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Record W2112685446 · doi:10.1021/ja902205f

TfNH<sub>2</sub> as Achiral Hydrogen-Bond Donor Additive to Enhance the Selectivity of a Transition Metal Catalyzed Reaction. Highly Enantio- and Diastereoselective Rhodium-Catalyzed Cyclopropanation of Alkenes Using α-Cyano Diazoacetamide

2009· article· en· W2112685446 on OpenAlexaff
David Marcoux, Soula Azzi, André B. Charette

Bibliographic record

VenueJournal of the American Chemical Society · 2009
Typearticle
Languageen
FieldChemistry
TopicCyclopropane Reaction Mechanisms
Canadian institutionsUniversité de Montréal
FundersUniversities Space Research Association
KeywordsChemistryCyclopropanationRhodiumCatalysisSelectivityTransition metalHydrogen bondTransition stateHydrogenCombinatorial chemistryMedicinal chemistryOrganic chemistryMolecule

Abstract

fetched live from OpenAlex

A highly stereoselective (up to 98% ee and 99:1 dr) Rh(II)-catalyzed formation of nitrile-substituted cyclopropanes is described. Alpha-cyano diazoacetamide reagents react with a variety of mono- and disubstituted olefins in good yields and excellent enantio- and diastereocontrol. Less reactive substrates, such as aliphatic olefins, also undergo the reaction. This new methodology features the unprecedented use of an achiral hydrogen-bond donor additive to enhance the selectivity and exploits the powerful trans-directing ability of amides solving the diastereocontrol issue of the formation of substituted 1-cyanocyclopropane-1-carboxy derivatives.

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: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.001
Threshold uncertainty score0.004

Distilled classifier scores by category (both heads)

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 science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0010.001

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 head0.006
GPT teacher head0.244
Teacher spread0.237 · 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 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

Citations113
Published2009
Admission routes1
Has abstractyes

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Same venueJournal of the American Chemical SocietySame topicCyclopropane Reaction MechanismsFrench-language works237,207