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Enantioselective Construction of Alkylated Stereogenic Centers

2011· book-chapter· en· W4238184666 on OpenAlexaboutno aff
Douglass F. Taber

Bibliographic record

VenueOxford University Press eBooks · 2011
Typebook-chapter
Languageen
FieldChemistry
TopicAsymmetric Hydrogenation and Catalysis
Canadian institutionsnot available
Fundersnot available
KeywordsEnantioselective synthesisStereocenterChemistryAlkylationConjugateAlkeneMichael reactionCarbanionStereochemistryOrganic chemistryCatalysisMathematics

Abstract

fetched live from OpenAlex

The enantioselectivity of alkene reduction usually depends on the geometric purity of the alkene. Bruce H. Lipshutz of the University of California, Santa Barbara used ( Organic Lett. 2007, 9, 4713) carboalumination of the alkyne 1 to prepare 2, which was selectively reduced to 3 in high ee. André B. Charette of the Université de Montréal reported ( Angew. Chem. Int. Ed. 2007, 46, 5955) a related reduction of unsaturated sulfones such as 4. Juan C. Carretero of the Universidad Autónoma de Madrid has developed ( J. Org. Chem. 2007, 72, 9924) a complementary route to enantiomerically-enriched sulfones, by conjugate addition to the unsaturated pyridyl sulfone 6 . Specifically for styrene derivatives, Hans-Günther Schmalz of the University of Cologne has shown (Organic Lett. 2007, 9, 3555) that the product 11 from enantioselective Rh-catalyzed hydroboration can be homologated to 13. Conjugate addition of stabilized carbanions can also be carried out with high enantiocontrol. David A. Evans of Harvard University has described (J. Am. Chem. Soc. 2007, 129, 11583) the Ni-catalyzed addition of malonate 15 to nitroalkenes such as 14. Claudio Palomo of the Universidad de País Vasco (Angew. Chem. Int. Ed. 2007, 46, 8431) and concurrently Yujiro Hayashi of the Tokyo University of Science (Organic Lett. 2007, 9, 5307) have developed organocatalytic protocols for the addition of nitromethane 18 to unsaturated aldehydes such as 17. J. Michael Chong of the University of Waterloo has found (J. Am. Chem. Soc. 2007, 129, 4908) that the Binol-mediated enantioselective conjugate addition of alkenylboronic acids such as 22 required the additional activation of the aryl ketone. Shun-Jun Li of Suzhou University and Teck-Peng Loh of Nanyang Technical University have extended (J. Am. Chem. Soc. 2007, 129, 276) enantioselective conjugate to unsaturated esters such as 24 to more highly substituted Grignard reagents. Alexandre Alexakis of the University of Geneva has demonstrated (Tetrahedron Lett. 2007, 48, 7408) that Ac2O is compatible with Et2 Zn conjugate addition conditions, leading directly to the trapped enolate 27. Selective cleavage of 27 can then be used to prepare acyclic derivatives.

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 machine prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: metacan-v3-hybrid-931329e0061cValidation 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 score0.002
Threshold uncertainty score0.007

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.001
Research integrity0.0000.001
Insufficient payload (model declined to judge)0.0020.001

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 head0.017
GPT teacher head0.182
Teacher spread0.165 · 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 source (direct Gemma or distilled Codex), 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

Citations0
Published2011
Admission routes1
Has abstractyes

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