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Record W3152248638 · doi:10.1002/anie.202103327

Direct Synthesis of Ketones from Methyl Esters by Nickel‐Catalyzed Suzuki–Miyaura Coupling

2021· article· en· W3152248638 on OpenAlex
Yan‐Long Zheng, Pei‐Pei Xie, Omid Daneshfar, K. N. Houk, Xin Hong, Stephen G. Newman

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

VenueAngewandte Chemie International Edition · 2021
Typearticle
Languageen
FieldChemistry
TopicCatalytic Cross-Coupling Reactions
Canadian institutionsUniversity of Ottawa
FundersFundamental Research Funds for the Central UniversitiesNational Natural Science Foundation of ChinaCanada Foundation for InnovationState Key Laboratory of Clean Energy UtilizationBASF
KeywordsChemoselectivityArylChemistryCatalysisNucleophileReactivity (psychology)Catalytic cycleAlkylCarbeneEtherAmideNickelBond cleavageCoupling reactionLigand (biochemistry)Combinatorial chemistryFunctional groupMedicinal chemistryOrganic chemistry

Abstract

fetched live from OpenAlex

Abstract The direct conversion of alkyl esters to ketones has been hindered by the sluggish reactivity of the starting materials and the susceptibility of the product towards subsequent nucleophilic attack. We have now achieved a cross‐coupling approach to this transformation using nickel, a bulky N‐heterocyclic carbene ligand, and alkyl organoboron coupling partners. 65 alkyl ketones bearing diverse functional groups and heterocyclic scaffolds have been synthesized with this method. Catalyst‐controlled chemoselectivity is observed for C(acyl)−O bond activation of multi‐functional substrates bearing other bonds prone to cleavage by Ni, including aryl ether, aryl fluoride, and N‐Ph amide functional groups. Density functional theory calculations provide mechanistic support for a Ni 0 /Ni II catalytic cycle and demonstrate how stabilizing non‐covalent interactions between the bulky catalyst and substrate are critical for the reaction's success.

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 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 score0.004
Threshold uncertainty score1.000

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)0.0030.000

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 head0.013
GPT teacher head0.265
Teacher spread0.252 · 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