Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Total Synthesis of Gelsenicine via a Catalyzed Cycloisomerization Strategy.

ABSTRACT: The first total synthesis of (±)-gelsenicine is reported. The synthetic route is highly efficient (13 steps), featuring (1) a pivotal metal-catalyzed isomerization/rearrangement process that forges the central core of the molecule and (2) two facile C-N bond-forming steps that establish the flanking heterocycles.

SUBMITTER: Newcomb ET

PROVIDER: S-EPMC4732274 | biostudies-literature | 2016 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Total Synthesis of Gelsenicine via a Catalyzed Cycloisomerization Strategy.

Newcomb Eric T ET Knutson Phil C PC Pedersen Blaine A BA Ferreira Eric M EM

Journal of the American Chemical Society 20151230 1

The first total synthesis of (±)-gelsenicine is reported. The synthetic route is highly efficient (13 steps), featuring (1) a pivotal metal-catalyzed isomerization/rearrangement process that forges the central core of the molecule and (2) two facile C-N bond-forming steps that establish the flanking heterocycles. ...[more]

PMID: 26716762

Similar Datasets

Effective synthesis of bicyclodienes via palladium-catalyzed asymmetric allylic alkylation and ruthenium-catalyzed cycloisomerization.

Project description:[n.3.0]Bicycles (n = 3-6) can be synthesized using palladium-catalyzed asymmetric allylic alkylation followed by ruthenium-catalyzed cycloisomerization. New types of triarylphosphino-1,2-diaminooxazoline ligands show the same high levels of enantioselectivity observed with Trost ligand when employed in Pd-catalyzed allylic alkylation reactions. The enyne products of these allylic alkylation reactions were further elaborated using a Ru-catalyzed redox isomerization process, for which a mechanism is proposed.

| S-EPMC7772093 | biostudies-literature

A racemic formal total synthesis of clavukerin A using gold(I)-catalyzed cycloisomerization of 3-methoxy-1,6-enynes as the key strategy.

Project description:An efficient formal total synthesis of (±)-clavukerin A was accomplished via a gold-catalyzed cycloisomerization of a 3-methoxy-1,6-enyne 5 as the key strategy followed by Rh-catalyzed stereoselective hydrogenation of the cycloheptenone 4.

| S-EPMC3135252 | biostudies-literature

Formal synthesis of 7-methoxymitosene and synthesis of its analog via a key PtCl2-catalyzed cycloisomerization.

Project description:A formal synthesis of 7-methoxymitosene is achieved via a key platinum-catalyzed cycloisomerization. The precursor for the Pt catalysis, a fully functionalized benzene intermediate, was prepared via a regioselective electrophilic bromination followed by a chemoselective Sonogashira cross-coupling. It underwent the PtCl2-catalyzed cycloisomerization smoothly despite its hindered and highly electron-rich nature. Analogs of 7-methoxymitosene can be accessed in an expedient manner by following a similar synthetic sequence.

| S-EPMC3488125 | biostudies-literature

Synthesis of Vicinal Quaternary All-Carbon Centers via Acid-catalyzed Cycloisomerization of Neopentylic Epoxides.

Project description:We report our studies on the development of a catalytic cycloisomerization of 2,2-disubstituted neopentylic epoxides to produce highly substituted tetralins and chromanes. Termination of the sequence occurs via Friedel-Crafts-type alkylation of the remote (hetero)arene linker. The transformation is efficiently promoted by sulfuric acid and proceeds best in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) as the solvent. Variation of the substitution pattern provided detailed insights into the migration tendencies and revealed a competing disproportionation pathway of dihydronaphthalenes.

| S-EPMC7115968 | biostudies-literature

Stereoselective Synthesis of Exocyclic Tetrasubstituted Vinyl Halides via Ru-Catalyzed Halotropic Cycloisomerization of 1,6-Haloenynes.

Project description:Herein, a ruthenium-catalyzed cycloisomerization that transforms 1,6-haloenynes into 5-membered carbo- and heterocycles that bear exocyclic, stereodefined, tetrasubstituted vinyl halides is reported. The reaction is insensitive to air and water, tolerates a variety of functional groups, and proceeds with good to excellent stereoselectivity and yield.

| S-EPMC5726863 | biostudies-literature

Synthesis of a 1,3-Bridged Macrobicyclic Enyne via Chemoselective Cycloisomerization Using Palladium-Catalyzed Alkyne-Alkyne Coupling.

Project description:A unique intramolecular Pd-catalyzed alkyne-alkyne coupling is presented. This transformation generates a strained, 1,3-bridged, macrocyclic enyne. The process was readily executed on gram scale, and the structure of the product was elucidated via X-ray crystallographic analysis. A mechanistic rationale for the observed chemoselectivity is provided.

| S-EPMC5726859 | biostudies-literature

A nucleophile-catalyzed cycloisomerization permits a concise synthesis of (+)-harziphilone.

Project description:Substantial structural transformations of much use in complex chemical synthesis can be achieved by channeling the reactivity of highly unsaturated molecules. This report describes the direct conversion of an acyclic polyunsaturated diketone to the HIV-1 Rev/Rev-responsive element inhibitor harziphilone under mild reaction conditions.

| S-EPMC514435 | biostudies-literature

Total synthesis of (+)-pilosinine via a stereodivergent conjugate addition strategy.

Project description:In recent work, asymmetric conjugate addition reactions to chiral 4-phenyl-N-enoyl-1,3-oxazolidinones have been shown to give different stereochemical outcomes depending on the conditions employed. Through the application of stereodivergent reaction conditions, the total synthesis of (+)-pilosinine and the formal synthesis of (-)-pilosinine has been completed from a single enantiomer of the 1,3-oxazolidi-none auxiliary.

| S-EPMC7288726 | biostudies-literature

Gold-Catalyzed Regioselective Synthesis of Crowded Cyclopentadienes by Migratory Cycloisomerization of Vinylallenes.

Project description:We report the regioselective synthesis of silyl-substituted cyclopentadienyl esters through gold-catalyzed migratory cycloisomerization of silyl-substituted vinylallenes. This transformation is proposed to proceed through a perfectly orchestrated sequence of events including Nazarov-like cyclization and several silyl and hydrogen rearrangements. Furthermore, exploiting the multifaceted nature of the gold catalyst, we have also identified suitable conditions for the synthesis of these cyclopentadienes in a more straightforward manner through gold-catalyzed reaction of propargyl esters and alkynylsilanes.

| S-EPMC9490818 | biostudies-literature

Gold(i)-catalyzed cycloisomerization of vinylidenecyclopropane-enes via carbene or non-carbene processes.

Project description:Gold catalyzed cycloisomerization of aromatic ring tethered vinylidenecyclopropane-enes provides a divergent synthetic protocol for the construction of O-containing fused heterocycles through controllable carbene or non-carbene related processes. The carbene induced process features a new amphiphilic strategy to generate a gold carbene via a rearrangement of vinylidenecyclopropane. Whereas, the electronic effect of the ortho-substituents switches the reaction mode onto the non-carbene related process, from which five- or six-membered rings are selectively produced through allyl-migration.

| S-EPMC5949847 | biostudies-other

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data