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Record W4414622770 · doi:10.1021/jacs.5c13001

Overriding Norrish Type II to Access Cyclopropanols

2025· article· en· W4414622770 on OpenAlexafffund
James W. Pearson, Samantha L. Dudra, Anthony F. Palermo, B Chiu, Julie Dang, Alexis L. Gabbey, Bridget A. B. Henson, Teh Ren Hou, Sophie A. L. Rousseaux

Bibliographic record

VenueJournal of the American Chemical Society · 2025
Typearticle
Languageen
FieldChemistry
TopicRadical Photochemical Reactions
Canadian institutionsUniversity of Toronto
FundersNatural Sciences and Engineering Research Council of CanadaCanada Research ChairsGovernment of OntarioUniversity of TorontoCanada Foundation for InnovationOntario Research Foundation
KeywordsArylRing (chemistry)PopulationAtom (system on chip)Carbonyl groupFunctional group

Abstract

fetched live from OpenAlex

The propensity for photoexcited aryl ketones to undergo 1,5-hydrogen atom transfer (HAT) reactions is a fundamental process in organic synthesis and polymer degradation. Since its discovery in 1958, Norrish-Yang photocyclization has become a prominent method to access cyclobutanols under mild photoirradiative conditions. Despite its successful extension to larger ring systems, access to medicinally relevant 3-membered rings remains limited due to the strong kinetic preference for 1,5-HAT over 1,4-HAT. In this work, we demonstrate the first photocyclization of β-boryl aryl ketones to cyclopropanols. Our strategy relies on solvent-controlled selective population of the π,π* triplet state over the n,π* triplet state, with the former preferentially undergoing 1,4-boryl group transfer over 1,5-HAT. This protocol proceeds under mild irradiative conditions with excellent functional group tolerance, providing access to a broad range of highly valuable cyclopropanol scaffolds.

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)0.001
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 score0.038
Threshold uncertainty score0.495

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.001
Bibliometrics0.0000.001
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.001
Research integrity0.0000.001
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 head0.014
GPT teacher head0.311
Teacher spread0.298 · 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 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

Citations9
Published2025
Admission routes2
Has abstractyes

Explore more

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