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Carbon–Carbon Bond Formation: The Petrov Synthesis of Combretastatin A-4

2015· book-chapter· en· W3106530464 on OpenAlexaboutno aff
Douglass F. Taber

Bibliographic record

VenueOxford University Press eBooks · 2015
Typebook-chapter
Languageen
FieldChemistry
TopicSynthetic Organic Chemistry Methods
Canadian institutionsnot available
Fundersnot available
KeywordsChemistryNitrileSilylationAcetalAldehydeAcetonitrileMedicinal chemistryPolymer chemistryCatalysisStereochemistryOrganic chemistry

Abstract

fetched live from OpenAlex

Janine Cossy of ESPCI Paris (Org. Lett. 2011, 13, 4084) and Yasushi Obora of Kansai University (Chem. Lett. 2011, 40, 1055) independently developed conditions for the “borrowed hydrogen” condensation of acetonitrile with an alcohol 1 to give the nitrile 2. Akio Baba of Osaka University showed (Angew. Chem. Int. Ed. 2011, 50, 8623) that a ketene silyl acetal 4 could be condensed with a carboxylic acid 3 to give the β-keto ester 5. Timothy W. Funk of Gettysburg College found (Tetrahedron Lett. 2010, 51, 6726) that the cyclopropanol 6, readily prepared by Kulinkovich condensation of an alkene with an ester, opened with high regioselectivity to give the branched ketone 7. In an elegant application of C–H functionalization, Yong Hae Kim of KAIST and Kieseung Lee of Woosuk University added (Tetrahedron Lett. 2011, 52, 4662) the acetal 9 in a conjugate sense to 8 to give 10. Hitoshi Kuniyasu and Nobuaki Kambe of Osaka University devised (Tetrahedron Lett. 2010, 51, 6818) conditions for the Pd-catalyzed carbonylation of a silyl alkyne 11 to the ester 12 with high geometric control. Dennis G. Hall of the University of Alberta also observed (Chem. Sci. 2011, 2, 1305) good geometric control in the rearrangement of the vinyl carbinol 13 to the alcohol 14. Takashi Tomioka of the University of Mississippi condensed (J. Org. Chem. 2011, 76, 8053) the anion 16, prepared in situ from lithio acetonitrile and 1-iodobutane, with the aldehyde 15 to give a nitrile, which was carried onto the aldehyde 17, again with good control of geometry. Bruce H. Lipshutz of the University of California, Santa Barbara established (Org. Lett. 2011, 13, 3818) conditions for the Negishi coupling of an alkenyl halide 18 to give 20 with retention of alkene geometry. Daesung Lee of the University of Illinois, Chicago found (J. Am. Chem. Soc. 2011, 133, 12964) that a Pt catalyst rearranged a silyl cyclopropene 21 to the allene 22. Jan Deska of the Universität zu Köln prepared (Angew. Chem. Int. Ed. 2011, 50, 9731) the enantiomerically enriched allene 25 by lipase-mediated esterification of the prochiral 23.

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 categoriesMeta-epidemiology (narrow)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Not applicable · Consensus signal: none
GenreCandidate signal: Other · Consensus signal: Other
Teacher disagreement score0.796
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.001
Research integrity0.0010.001
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 head0.036
GPT teacher head0.227
Teacher spread0.191 · 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 designNot applicable
Domainnot available
GenreOther

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
Published2015
Admission routes1
Has abstractyes

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