Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
A nickel-catalyzed reductive tandem cyclization of the elaborated β-bromo acetal with a dibenzoxepin scaffold was invented to strategically construct the remaining two rings in linoxepin. The generated diasterodivergent intermediates could be easily converted to both enantiomers of this unique cyclolignan molecule facile oxidations, thus realizing enantiodivergent total synthesis of linoxepin for the first time.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d3cc05312a | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Intramolecular Ni-catalyzed reductive coupling enables enantiodivergent synthesis of linoxepin.
Chem Commun (Camb)
January 2024
School of Chemistry, Key Laboratory of Advanced Technologies of Materials (Ministry of Education), Southwest Jiaotong University, Chengdu 610031, P. R. China.
Article Synopsis
- - A new nickel-catalyzed method was developed to create the final two rings of the complex molecule linoxepin using a β-bromo acetal and dibenzoxepin.
- - This process produced intermediates that could be transformed into both enantiomers of linoxepin, showcasing the versatility of the method.
- - The research achieved the first total synthesis of linoxepin with an enantiodivergent approach, allowing easy access to both forms of the compound.
Total synthesis of linoxepin facilitated by a Ni-catalyzed tandem reductive cyclization.
Chem Commun (Camb)
June 2022
Sichuan Engineering Research Center for Biomimetic Synthesis of Natural Drugs, School of Life Science and Engineering, Southwest Jiaotong University, Chengdu 610031, People's Republic of China.
A nickel-catalyzed reductive cyclization was developed to construct the tricyclic core embedded in linoxepin, a cyclolignan with a unique benzoxepin ring. The generated diastereodivergent acetals could be converted to the common unsaturated lactone, thus allowing a racemic synthesis of this molecule after incorporation of the remaining aromatic ring. This strategy with a late-stage installation of the D-ring led to the facile production of several linoxepin analogs as well.
View Article and Find Full Text PDFAsymmetric Total Synthesis of Aglacins A, B, and E.
Angew Chem Int Ed Engl
July 2021
Shanghai Key Laboratory of Green Chemistry and Chemical, Processes, School of Chemistry and Molecular Engineering, East China Normal University, China.
An asymmetric photoenolization/Diels-Alder (PEDA) reaction between electron-rich 2-methylbenzaldehydes and unsaturated γ-lactones was developed to directly construct the basic tricyclic core of aryltetralin lactone lignans. This methodology enabled the first asymmetric total synthesis of aglacins A, B, and E and revision of the absolute configuration of these natural lignans. The strategy was also used to prepare the naturally occurring aryldihydronaphthalene-type lignans (-)-7,8-dihydroisojusticidin B and (+)-linoxepin in four and six steps, as well as 27 natural-product-like molecules containing a C8' quaternary center.
View Article and Find Full Text PDFOrigin of stereocontrol in guanidine-bisurea bifunctional organocatalyst that promotes α-hydroxylation of tetralone-derived β-ketoesters: asymmetric synthesis of β- and γ-substituted tetralone derivatives via organocatalytic oxidative kinetic resolution.
J Am Chem Soc
February 2015
Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, 2-24-16, Naka-cho, Koganei city, 184-8588, Tokyo Japan.
The mechanism of asymmetric α-hydroxylation of tetralone-derived β-ketoesters with guanidine-bisurea bifunctional organocatalyst in the presence of cumene hydroperoxide (CHP) was examined by means of DFT calculations to understand the origin of the stereocontrol in the reaction. The identified transition-state model was utilized to design an enantioselective synthesis of β- or γ-substituted tetralones by catalytic oxidative kinetic resolution reaction of tetralone-derived β-ketoesters. This kinetic resolution reaction proceeded with high selectivity, and selectivity factors (s value) of up to 99 were obtained.
View Article and Find Full Text PDFEnantioselective total synthesis of the lignan (+)-linoxepin.
Chemistry
December 2014
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstrasse 2, 37077 Göttingen (Germany).
An enantioselective total synthesis of the natural (+)-linoxepin (1) was accomplished in eleven steps from bromovanin (24). Key steps are a domino carbopalladation/ Mizoroki-Heck reaction with the formation of a pentacyclic system, an asymmetric hydroboration as well as an oxidative lactonization.
View Article and Find Full Text PDF