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Record W4286489322 · doi:10.1021/acscatal.2c02233

Desulfonylative Coupling of Alkylsulfones with <i>gem-</i>Difluoroalkenes by Visible-Light Photoredox Catalysis

2022· article· en· W4286489322 on OpenAlex

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

VenueACS Catalysis · 2022
Typearticle
Languageen
FieldChemistry
TopicRadical Photochemical Reactions
Canadian institutionsQueen's University
FundersJapan Society for the Promotion of ScienceNatural Sciences and Engineering Research Council of CanadaMinistry of Education, Culture, Sports, Science and TechnologyCanada Foundation for Innovation
KeywordsIsomerizationPhotoredox catalysisChemistryPhotoisomerizationCatalysisIntramolecular forceSelectivityStereoselectivityPhotochemistrySubstrate (aquarium)AlkylElectron transferCombinatorial chemistryStereochemistryOrganic chemistryPhotocatalysis

Abstract

fetched live from OpenAlex

The desulfonylative radical addition of tertiary alkyl groups to gem-difluoroalkenes by photoredox Ir-catalyst is described. This method exhibits broad substrate scope, affording structurally diverse (E)-fluoroalkene derivatives in a highly stereoselective manner. The resulting (E)-fluoroalkenes were converted into complex fused cyclic compounds by intramolecular cyclization reactions. Control experiments and theoretical calculations are consistent with a single Ir catalyst playing the dual role of generating radical species from sulfones via single electron transfer and mediating Z/E isomerization via energy transfer. A subset of fluoroalkenes provided Z stereoisomers with >90% selectivity, but the same alkenes could also be obtained as E isomers with high selectivity by taking advantage of a secondary Z to E photoisomerization.

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)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
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 score0.011
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.002
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0020.000

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 head0.006
GPT teacher head0.212
Teacher spread0.206 · 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