Evidence map›Paper›PMID 26385263›Full record

ArticleAngewandte Chemie (International ed. in English)2015

Synthesis of ent-ketorfanol via a C-H alkenylation/torquoselective 6π electrocyclization cascade.

Eric M Phillips, Tehetena Mesganaw, Ashay Patel, Simon Duttwyler, Brandon Q Mercado, Kendall N Houk, Jonathan A Ellman

Abstract read
PubMed Full text at PMC Publisher
In one paragraph

Article in Angewandte Chemie (International ed. in English), 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 5 papers.

0numbers the graph read from it
0cells of the map it votes in
5citing papers in PubMed
–field-weighted citation impact
1 · What the graph read from it

What it found

Each row is one number read from the abstract, on the scale the paper reported it, with its interval. Left of the dashed line favours the treatment, right favours the comparator. Under each row is the sentence it came from. New to these charts? A ten-minute tutorial.

The abstract states no effect estimate the extractor could read, or names no intervention and outcome on the map, so this paper lights no cell and moves no belief. It is still indexed, cited and linked below.

2 · The registry

The trial behind it

Trials whose registry record cites this paper, or whose number appears in the abstract. A trial that started after this paper was published is citing it as background, not reporting it.

Neither the registry nor the abstract names a trial number. If this is a trial report, that itself is worth knowing.

3 · Its place in the literature

Who cites it

5 citing papers in PubMed.

  1. Article
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4 · The record

Corrections and comments

PubMed lists nothing against this paper. Absence here is not a guarantee, only a check that was made.

5 · Who and what money

Authors and funding

7 authors.

Eric M PhillipsDepartment of Chemistry, Yale University, 225 Prospect St., New Haven, CT 06520 (USA).
Tehetena MesganawDepartment of Chemistry, Yale University, 225 Prospect St., New Haven, CT 06520 (USA).
Ashay PatelDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA).
Simon DuttwylerDepartment of Chemistry, Yale University, 225 Prospect St., New Haven, CT 06520 (USA).
Brandon Q MercadoDepartment of Chemistry, Yale University, 225 Prospect St., New Haven, CT 06520 (USA).
Kendall N HoukDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569 (USA). houk@chem.ucla.edu.
Jonathan A EllmanDepartment of Chemistry, Yale University, 225 Prospect St., New Haven, CT 06520 (USA). jonathan.ellman@yale.edu.

Funding

CHEMISTRY BIOLOGY INTERFACE TRAINING PROGRAMT32GM008496 · NIGMS · UNIVERSITY OF CALIFORNIA LOS ANGELES · PI MAYNARD, HEATHER D · 1993 to 2019
$6.3M
C-H Functionalization for the Synthesis of Amines and Nitrogen HeterocyclesR01GM069559 · NIGMS · YALE UNIVERSITY · PI ELLMAN, JONATHAN A · 2004 to 2017
$5.4M
STEREOSELECTIVITIES OF SYNTHETIC ORGANIC REACTIONSR01GM036700 · NIGMS · UNIVERSITY OF CALIFORNIA LOS ANGELES · PI HOUK, KENDALL N · 1986 to 2013
$2.4M
STEREOSELECTIVITIES OF SYNTHETIC ORGANIC REACTIONSR37GM036700 · NIGMS · UNIVERSITY OF CALIFORNIA LOS ANGELES · PI HOUK, KENDALL N · 1997 to 2005
$1.5M
A Three-Component Annulation Reaction via Directed C-H ActivationF32GM090661 · NIGMS · YALE UNIVERSITY · PI PHILLIPS, ERIC MATTHEW · 2010 to 2012
$103k
NIGMS NIH HHS F32 GM090661NIGMS NIH HHS F32GM090661NIGMS NIH HHS GM 008496NIGMS NIH HHS GM069559NIGMS NIH HHS GM36700NIGMS NIH HHS R01 GM036700NIGMS NIH HHS R01 GM069559NIGMS NIH HHS R37 GM036700NIGMS NIH HHS T32 GM008496
6 · The paper itself

Abstract

The asymmetric synthesis of ent-ketorfanol from simple and commercially available precursors is reported. A Rh(I) -catalyzed intramolecular CH alkenylation/torquoselective 6π electrocyclization cascade provides a fused bicyclic 1,2-dihydropyridine as a key intermediate. Computational studies were performed to understand the high torquoselectivity of the key 6π electrocyclization. The computational results demonstrate that a conformational effect is responsible for the observed selectivity. The ketone functionality and final ring are introduced in a single step by a redox-neutral acid-catalyzed rearrangement of a vicinal diol to give the requisite carbonyl, followed by intramolecular Friedel-Crafts alkylation.

Indexed as

AlkenesAnalgesics, OpioidCatalysisCyclizationDihydropyridinesModels, MolecularOxidation-ReductionRhodiumStereoisomerism1,4-dihydropyridineAlkenesAnalgesics, OpioidDihydropyridinesent-ketorfanolRhodiumalkaloidsasymmetric synthesisCH activationheterocyclestorquoselectivity

Identifiers

PMID26385263
PMCPMC4676713

What OpenQuestion holds

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Registered trials

None linked

Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.