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Record W2003403540 · doi:10.1139/v03-141

The use of a chiral borate counteranion as a <sup>1</sup>H NMR shift reagent for cationic copper(I) complexes

2003· article· en· W2003403540 on OpenAlexvenueno aff
David B. Llewellyn, Bruce A. Arndtsen

Bibliographic record

VenueCanadian Journal of Chemistry · 2003
Typearticle
Languageen
FieldChemistry
TopicMolecular spectroscopy and chirality
Canadian institutionsnot available
Fundersnot available
KeywordsChemistryEnantiopure drugReagentOxazolineEnantiomerCopperCationic polymerizationProton NMRMedicinal chemistryLigand (biochemistry)StereochemistryOrganic chemistryEnantioselective synthesisCatalysis

Abstract

fetched live from OpenAlex

The chiral borate counteranion bis[(R)-1,1′-bi-2-naphtholato]borate (1 – ) has been found to be a competent chiral 1 H NMR shift reagent for cationic copper(I) complexes. This has been demonstrated by the addition of the Cu(NCMe) 4 + salt of 1 – to two classes of common chiral ligands in asymmetric catalysis: 2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl (tol-BINAP) (2) and 2,2′-isopropylidenebis(4-phenyl-2-oxazoline) (3). In the case of ligand 2, the addition of 1 equiv. of either (R,R)-2 or (S,S)-2 to Cu(NCMe) 4 + 1 – results in well-resolved 1 H NMR resonances for the two enantiomers. Examination of standard solutions of non-enantiopure 2 shows that the copper complex can be an effective NMR shift reagent of a wide range of enantiomeric compositions. Cu(NCMe) 4 + 1 – also generates distinct 1 H NMR resonances for the two separate enantiomers of 2,2′-isopropylidenebis(4-phenyl-2-oxazoline) (3). However, attempts to employ this copper salt as a chiral NMR shift reagent for rac-3 led to the discovery of a new and unexpected equilibrium: [(R,R)-3]Cu + + [(S,S)-3]Cu + [Formula: see text] [(R,R)-3][(S,S)-3]Cu + + Cu + . Key words: chiral counteranion, copper, chiral NMR shift reagent, ion pairing.

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)0.000
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 score0.137
Threshold uncertainty score0.620

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
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)0.0000.000

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 head0.022
GPT teacher head0.248
Teacher spread0.226 · 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

Citations12
Published2003
Admission routes1
Has abstractyes

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