Browse
Submit Data
Databases
API
Help

Dataset Information

34 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Catalytic Alkene Cyclization Reactions for the Stereoselective Synthesis of Complex "Terpenoid-like" Heterocycles.

ABSTRACT: A new catalytic synthesis of densely-substituted tetrahydroquinolines is described. This reaction forms up to two rings, three bonds, and three stereogenic centers with excellent stereo- and regiocontrol in a single step. Although control experiments demonstrate that the active catalyst is protic acid, Sc(OTf)3 serves as an effective and practical pre-catalyst. The scope of this reaction is demonstrated with 21 monocyclizations and 14 bicyclization reactions.

SUBMITTER: Moore JT

PROVIDER: S-EPMC3614375 | biostudies-literature | 2013 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Catalytic Alkene Cyclization Reactions for the Stereoselective Synthesis of Complex "Terpenoid-like" Heterocycles.

Moore Jared T JT Soldi Cristian C Fettinger James C JC Shaw Jared T JT

Chemical science 20121025 1

A new catalytic synthesis of densely-substituted tetrahydroquinolines is described. This reaction forms up to two rings, three bonds, and three stereogenic centers with excellent stereo- and regiocontrol in a single step. Although control experiments demonstrate that the active catalyst is protic acid, Sc(OTf)<sub>3</sub> serves as an effective and practical pre-catalyst. The scope of this reaction is demonstrated with 21 monocyclizations and 14 bicyclization reactions. ...[more]

PMID: 23565327

Similar Datasets

Synthesis of polycyclic nitrogen heterocycles via alkene aminopalladation/carbopalladation cascade reactions.

Project description:A new method for the synthesis of tricyclic nitrogen heterocycles from N,2-diallylaniline derivatives is described. These transformations proceed via sequential alkene aminopalladation of an intermediate L(n)Pd(Ar)(NRR') species followed by alkene carbopalladation of the resulting L(n)Pd(Ar)(R) complex. Both alkene insertion steps occur in preference to C-N or C-C bond-forming reductive elimination. An unusual 1,3-palladium shift occurs when 2-Allyl-N-(2-vinylphenyl)aniline is employed as substrate, which yields a tetracyclic molecule with three contiguous stereocenters.

| S-EPMC2830278 | biostudies-literature

Synthesis of (+)-discodermolide by catalytic stereoselective borylation reactions.

Project description:The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides an inspiration for new reaction development. A new synthesis of discodermolide employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for the alkylation of chiral enolates. Furthermore, this synthesis of discodermolide provides the first examples of the asymmetric 1,4-diboration of dienes and borylative diene-aldehyde couplings in complex-molecule synthesis.

| S-EPMC4171733 | biostudies-literature

Synthesis of Polycyclic Nitrogen Heterocycles via Cascade Pd-Catalyzed Alkene Carboamination/Diels-Alder Reactions.

Project description:Cascade Pd-catalyzed alkene carboamination/Diels-Alder reactions between bromodienes and amines bearing two pendant alkenes are described. These transformations generate 4 bonds, 3 rings, and 3-5 stereocenters to afford polycyclic nitrogen heterocycles with high diastereoselectivity.

| S-EPMC4480637 | biostudies-literature

Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer.

Project description:Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis?aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence.

| S-EPMC3324620 | biostudies-literature

Convergent Synthesis of Diverse Nitrogen Heterocycles via Rh(III)-Catalyzed C-H Conjugate Addition/Cyclization Reactions.

Project description:The development of Rh(III)-catalyzed C-H conjugate addition/cyclization reactions that provide access to synthetically useful fused bi- and tricyclic nitrogen heterocycles is reported. A broad scope of C-H functionalization substrates and electrophilic olefin coupling partners is effective, and depending on the nature of the directing group, cyclic imide, amide, or heteroaromatic products are obtained. An efficient synthesis of a pyrrolophenanthridine alkaloid natural product, oxoassoanine, highlights the utility of this method.

| S-EPMC4973575 | biostudies-literature

Stereoselective isoxazolidine synthesis via copper-catalyzed alkene aminooxygenation.

Project description:Isoxazolidines are useful in organic synthesis, drug discovery, and chemical biology endeavors. A new stereoselective synthesis of methyleneoxy-substituted isoxazolidines is disclosed. The method involves copper-catalyzed aminooxygenation/cyclization of N-sulfonyl-O-butenyl hydroxylamines in the presence of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical (TEMPO) and O(2) and provides substituted isoxazolidines in excellent yields and diastereoselectivities. We also demonstrate selective mono N-O reduction followed by oxidation of the remaining N-O bond to reveal a 2-amino-?-lactone. Reduction of the ?-lactone reveals the corresponding aminodiol.

| S-EPMC3465949 | biostudies-literature

Stereoselective Synthesis of Isoxazolidines via Copper-Catalyzed Alkene Diamination.

Project description:A convenient copper-catalyzed intramolecular/intermolecular alkene diamination reaction to synthesize 3-aminomethyl-functionalized isoxazolidines under mild reaction conditions and with generally high levels of diastereoselectivity was achieved. This reaction demonstrates that previously underutilized unsaturated carbamates are good [Cu]-catalyzed diamination substrates. Sulfonamides, anilines, benzamide, morpholine, and piperidine can serve as the external amine source. This relatively broad amine range is attributed to the mild reaction conditions. Reduction of the N-O bond could also be achieved, revealing the corresponding 3,4-diamino-1-alcohols efficiently.

| S-EPMC5944859 | biostudies-literature

Remarkable Alkene-to-Alkene and Alkene-to-Alkyne Transfer Reactions of Selenium Dibromide and PhSeBr. Stereoselective Addition of Selenium Dihalides to Cycloalkenes.

Project description:The original goal of this research was to study stereochemistry of selenium dihalides addition to cycloalkenes and properties of obtained products. Remarkable alkene-to-alkene and alkene-to-alkyne transfer reactions of selenium dibromide and PhSeBr were discovered during this research. The adducts of selenium dibromide with alkenes or cycloalkenes easily exchange SeBr2 with other unsaturated compounds, including acetylenes, at room temperature, in acetonitrile. Similar alkene-to-alkene and alkene-to-alkyne transfer reactions of the PhSeBr adducts with alkenes or cycloalkenes take place. The supposed reaction pathway includes the selenium group transfer from seleniranium species to alkenes or alkynes. It was found that the efficient SeBr2 and PhSeBr transfer reagents are Se(CH2CH2Br)2 and PhSeCH2CH2Br, which liberate ethylene, leading to a shift in equilibrium. The regioselective and stereoselective synthesis of bis(E-2-bromovinyl) selenides and unsymmetrical E-2-bromovinyl selenides was developed based on the SeBr2 and PhSeBr transfer reactions which proceeded with higher selectivity compared to analogous addition reactions of SeBr2 and PhSeBr to alkynes under the same conditions.

| S-EPMC6983007 | biostudies-literature

Stereoselective cascade reactions that incorporate a 7-exo acyl radical cyclization.

Project description:[reaction: see text] Radical cascades that feature a 7-exo acyl radical cyclization followed by a 6-exo or 5-exo alkyl radical cyclization proceed with very good yields and diastereoselectivities. Two stereocenters are created by the reaction, and a single isomeric product was obtained from each of the five substrates examined. The relative configurations of the products are consistent with cyclizations occurring via chairlike or pseudochairlike transition states.

| S-EPMC2517416 | biostudies-literature

Catalytic platinum-initiated cation-olefin reactions with alkene terminating groups.

Project description:A series of phosphine-Pt(2+)-catalysts is reported, which enable the oxidative cascade cyclization of poly-alkene substrates. When the terminus is appropriately arranged and a catalyst reoxidation mediator is included, several polycyclic all carbon skeletons can be obtained. In one example, a chiral P2Pt(+2) catalyst provides up to 79% ee.

| S-EPMC3786443 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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