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Record W4410501014 · doi:10.1002/jcc.70130

Comparative Study of Predicting Radical CH Functionalization Sites in Nitrogen Heteroarenes Using a Radical General‐Purpose Reactivity Indicator and the Radical Fukui Function

2025· article· en· W4410501014 on OpenAlexfundno aff
Yoshio Barrera, James S. M. Anderson

Bibliographic record

VenueJournal of Computational Chemistry · 2025
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsnot available
FundersDirección General de Asuntos del Personal Académico, Universidad Nacional Autónoma de MéxicoAlliance de recherche numérique du CanadaConsejo Nacional de Ciencia y TecnologíaCompute Canada
KeywordsReactivity (psychology)ChemistryFukui functionMoleculeIsopropylNitrogenComputational chemistryRadicalHydroxyl radicalMedicinal chemistryOrganic chemistryElectrophileCatalysis

Abstract

fetched live from OpenAlex

ABSTRACT The Radical General‐Purpose Reactivity Indicator (R‐GPRI) is a valuable new tool for discerning the most reactive atoms within a molecule undergoing radical attack. In this study, we apply the condensed R‐GPRI and the condensed Radical Fukui Function (RFF) to identify the two most reactive atoms in 14 nitrogen heteroarenes subjected to radical attack by •CF 3 (trifluoromethyl radical) and • i ‐Pr (isopropyl radical). The results were compared with available experimental data and calculated activation barriers to comprehensively evaluate the reactivity of these molecules, especially in reactions without isolated products. The outcomes indicate that R‐GPRI is a robust alternative for identifying the most reactive CH sites in disubstituted nitrogen heteroarenes, outperforming the RFF. We also found that for nitrogen heteroarenes, summing the charges of the hydrogen atoms into the heavier atoms to which they are bonded as computed with the Hirshfeld population scheme enhances the performance of the RFF compared to previous findings. As such, the R‐GPRI appropriately incorporates both charge and RFF contributions. It is also observed that the atoms within molecules that have a small condensed RFF tend to be unreactive in these radical attack reactions. This is even observed in atoms with the largest charge in magnitude (with the appropriate sign) but a small condensed RFF.

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 categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Theoretical or conceptual · Consensus signal: none
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.709
Threshold uncertainty score0.502

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 science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

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 head0.017
GPT teacher head0.290
Teacher spread0.274 · 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.

The models applied no category: nothing in the taxonomy fit this work.
Study designTheoretical or conceptual
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

Citations2
Published2025
Admission routes1
Has abstractyes

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