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Record W3107060766 · doi:10.1055/s-0040-1705978

Shining Light on the Light-Bearing Element: A Brief Review of Photomediated C–H Phosphorylation Reactions

2020· review· en· W3107060766 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.

fundA Canadian funder is recorded on the work.
no affNo Canadian affiliation: this work is invisible to an affiliation-only frame.
No Canadian affiliation. An affiliation-only frame, the usual design, would never have seen this work. It is one of the works that make the case for inverting the frame.

Bibliographic record

VenueSynthesis · 2020
Typereview
Languageen
FieldChemistry
TopicRadical Photochemical Reactions
Canadian institutionsnot available
FundersFonds Québécois de la Recherche sur la Nature et les TechnologiesNatural Sciences and Engineering Research Council of CanadaCanada Research ChairsMcGill University
KeywordsChemistryRadicalNucleophilePhotoredox catalysisPhotochemistryArylReagentIonic bondingBond cleavageCombinatorial chemistryCatalysisAlkylOrganic chemistryPhotocatalysisIon

Abstract

fetched live from OpenAlex

Abstract Organophosphorus compounds have numerous useful applications, from versatile ligands and nucleophiles in the case of trivalent organophosphorus species to therapeutics, agrochemicals and material additives for pentavalent species. Although phosphorus chemistry is a fairly mature field, the construction of C–P(V) bonds relies heavily on either prefunctionalized substrates such as alkyl or aryl halides, or requires previously oxidized bonds such as C=N or C=O, leading to potential sustainability issues when looking at the overall synthetic route. In light of the recent advances in photochemistry, using photons as a reagent can provide better alternatives for phosphorylations by unlocking radical mechanisms and providing interesting redox pathways. This review will showcase the different photomediated phosphorylation procedures available for converting C–H bonds into C–P(V) bonds. 1 Introduction 1.1 Organophosphorus Compounds 1.2 Phosphorylation: Construction of C–P(V) Bonds 1.3 Photochemistry as an Alternative to Classical Phosphorylations 2 Ionic Mechanisms Involving Nucleophilic Additions 3 Mechanisms Involving Radical Intermediates 3.1 Mechanisms Involving Reactive Carbon Radicals 3.2 Mechanisms Involving Phosphorus Radicals 3.2.1 Photoredox: Direct Creation of Phosphorus Radicals 3.2.2 Photoredox: Indirect Creation of Phosphorus Radicals 3.2.3 Dual Catalysis 3.3 Photolytic Cleavage 4 Conclusion and Outlook

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)0.008
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: Other design · Consensus signal: none
GenreCandidate signal: Review · Consensus signal: Review
Teacher disagreement score0.806
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.008
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0020.001
Bibliometrics0.0000.001
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0060.000

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 head0.035
GPT teacher head0.295
Teacher spread0.260 · 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