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Record W2709360369 · doi:10.1021/acs.joc.7b00890

Atropisomerism in Tertiary Biaryl 2-Amides: A Study of Ar–CO and Ar–Ar′ Rotational Barriers

2017· article· en· W2709360369 on OpenAlexaff
Marianne Lorentzen, Indrek Kalvet, Françoise Sauriol, Toni Rantanen, Kåre B. Jørgensen, Victor Snieckus

Bibliographic record

VenueThe Journal of Organic Chemistry · 2017
Typearticle
Languageen
FieldChemistry
TopicAxial and Atropisomeric Chirality Synthesis
Canadian institutionsQueen's University
Fundersnot available
KeywordsAtropisomerChemistrySubstituentRotation (mathematics)Rotational transitionNuclear magnetic resonance spectroscopySubstitution (logic)CrystallographyStereochemistryComputational chemistryAngular momentum

Abstract

fetched live from OpenAlex

A rotational barrier study was performed on eight tertiary biaryl 2-amides using variable-temperature (VT) NMR and exchange (EXSY) spectroscopy experiments. Seven out of the eight 2-amido-2′-methylbiphenyls with additional 3- and 6-substitution patterns ( 1 – 7 ) were found to have approximately similar rotational barriers (Δ G ⧧ Tc = 56.5–67.5 kJ/mol). However, for both 3- and 6-substitution ( 8 ), the rotational barrier was found to be significantly higher (Δ G ⧧ = 102.6–103.8 kJ/mol). Computational studies performed on all eight compounds gave results in good agreement with the experimental rotational barriers. A transition state in which atropisomerism occurs by a cooperative rotation of the Ar–CO and Ar–Ar′ bonds depending on substituent location is proposed.

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 score0.002
Threshold uncertainty score0.007

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)0.0020.000

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 head0.010
GPT teacher head0.248
Teacher spread0.238 · 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

Citations16
Published2017
Admission routes1
Has abstractyes

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