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Record W2893885850 · doi:10.1002/ejoc.201801053

A Computational Determination of the Origins of Diastereoselective Alkylations of a Cysteinesulfenate Anion

2018· article· en· W2893885850 on OpenAlex
Adrian L. Schwan

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

VenueEuropean Journal of Organic Chemistry · 2018
Typearticle
Languageen
FieldChemistry
TopicSulfur-Based Synthesis Techniques
Canadian institutionsUniversity of Guelph
FundersNatural Sciences and Engineering Research Council of CanadaUniversity of Guelph
KeywordsChemistryStereoselectivityAlkylationLithium (medication)Density functional theoryHydrogen bondFunctional groupSulfenic acidCounterionMedicinal chemistryIonSteric effectsHydrogenComputational chemistryStereochemistryOrganic chemistryMoleculeCatalysisEnzyme

Abstract

fetched live from OpenAlex

Sulfenic acid anions (RSO – ) represent an untapped functional group for the formation of sulfoxides and other organic compounds. Their stereoselective alkylation is an important component of this chemistry, but factors governing reaction outcomes are not fully understood. The current study uses Density Functional Theory methods to break down the influencing roles of substituents attached to 2‐aminoethanesulfenate. The lithium counterion can be coordinated to pendant ester or carbamate carbonyl groups, whereas the sulfenate oxygen readily participates in hydrogen bonding with proximal hydrogen atoms of the (protected) amino group. A Moc‐protected, ester substituted, 2‐aminoethanesulfenate adopts both lithium coordination and hydrogen bonding in the lowest energy form and demonstrates stereoselective methylation and benzylation consistent with experiments from the literature.

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)0.001
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 score0.007
Threshold uncertainty score0.621

Codex and Gemma teacher scores by category

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

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 head0.011
GPT teacher head0.232
Teacher spread0.222 · 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