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Record W3084358376 · doi:10.1021/acscatal.0c02584

α-Tertiary Dialkyl Ether Synthesis via Reductive Photocatalytic α-Functionalization of Alkyl Enol Ethers

2020· article· en· W3084358376 on OpenAlexfundno aff
Jamie A. Leitch, Thomas Rossolini, Tatiana Rogova, Darren J. Dixon

Bibliographic record

VenueACS Catalysis · 2020
Typearticle
Languageen
FieldChemistry
TopicRadical Photochemical Reactions
Canadian institutionsnot available
FundersNatural Sciences and Engineering Research Council of CanadaJanssen PharmaceuticalsDefence Science and Technology LaboratorySyngenta InternationalAstex PharmaceuticalsDiamond Light SourceLeverhulme TrustVertex PharmaceuticalsRoyal Commission for the Exhibition of 1851GlaxoSmithKlineUCBEngineering and Physical Sciences Research CouncilAstraZenecaTakeda Pharmaceutical CompanyNovartisPfizer
KeywordsChemistryAlkeneEtherAlkylEnol etherEnolSurface modificationPhotochemistryCombinatorial chemistryOrganic chemistryWilliamson ether synthesisNucleophileCatalysis

Abstract

fetched live from OpenAlex

The photocatalytic construction of C(sp3)-rich α-tertiary dialkyl ethers through the reductive α-functionalization of alkyl enol ether substrates with conjugated alkenes in the presence of a Hantzsch ester terminal reductant under blue LED irradiation is described. Pivoting on oxocarbenium ion generation via an initial TMSCl-facilitated protic activation of the enol ether substrate, subsequent single-electron transfer to this intermediate delivers the putative nucleophilic α-oxy tertiary radical capable of productively combining with a variety of alkene substrates. The reductive functionalization strategy was simple to perform, efficient, broad in scope with respect to both alkene acceptor and enol ether donor fragments, and delivered a wide range of complex α-tertiary dialkyl ether architectures.

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 categoriesInsufficient 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 score0.027
Threshold uncertainty score0.998

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.001
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0030.000

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 head0.015
GPT teacher head0.234
Teacher spread0.218 · 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.

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

Citations40
Published2020
Admission routes1
Has abstractyes

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