Browse
Submit Data
Databases
API
Help

Dataset Information

43 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Formal Synthesis of (+)-Laurencin by Gold(I)-Catalyzed Intramolecular Dehydrative Alkoxylation.

ABSTRACT: 8-Membered cyclic ethers are found in a wide range of natural products; however, they are challenging synthetic targets due to enthalpic and entropic barriers. The gold(I)-catalyzed intramolecular dehydrative alkoxylation of ?-hydroxy allylic alcohols was explored to stereoselectively construct ?,?'-cis-oxocenes and further applied in a formal synthesis of (+)-laurencin. The gold(I)-catalyzed intramolecular dehydrative alkoxylation may constitute an alternative method for the synthesis of molecular building blocks and natural products that contain highly functionalized 8-membered cyclic ethers.

SUBMITTER: Lanier ML

PROVIDER: S-EPMC5653968 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Formal Synthesis of (+)-Laurencin by Gold(I)-Catalyzed Intramolecular Dehydrative Alkoxylation.

Lanier Megan L ML Park Hyeri H Mukherjee Paramita P Timmerman Jacob C JC Ribeiro Anthony A AA Widenhoefer Ross A RA Hong Jiyong J

Chemistry (Weinheim an der Bergstrasse, Germany) 20170503 30

8-Membered cyclic ethers are found in a wide range of natural products; however, they are challenging synthetic targets due to enthalpic and entropic barriers. The gold(I)-catalyzed intramolecular dehydrative alkoxylation of ω-hydroxy allylic alcohols was explored to stereoselectively construct α,α'-cis-oxocenes and further applied in a formal synthesis of (+)-laurencin. The gold(I)-catalyzed intramolecular dehydrative alkoxylation may constitute an alternative method for the synthesis of molecu ...[more]

PMID: 28393406

Similar Datasets

The regio- and stereospecific intermolecular dehydrative alkoxylation of allylic alcohols catalyzed by a gold(I) N-heterocyclic carbene complex.

Project description:A 1:1 mixture of [AuCl(IPr)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) and AgClO(4) catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to form allylic ethers. These transformations are regio- and stereospecific with preferential addition of the alcohol nucleophile at the ?-position of the allylic alcohol syn to the departing hydroxyl group and with predominant formation of the E stereoisomer. The minor ? regioisomer is formed predominantly through a secondary reaction manifold involving regioselective ?-alkoxylation of the initially formed allylic ether rather than by the direct ?-alkoxylation of the allylic alcohol.

| S-EPMC3882269 | biostudies-literature

Formal synthesis of salinosporamide A via NHC-catalyzed intramolecular lactonization.

Project description:An N-heterocyclic carbene (NHC) catalyzed intramolecular lactonization to prepare densely functionalized bicyclic γ-lactam-γ-lactone adducts from enals is reported. This method has been applied to the formal synthesis of salinosporamide A, a potent 20S proteasome inhibitor and anti-cancer therapeutic.

| S-EPMC2896295 | biostudies-literature

Gold(I)-catalyzed synthesis of γ-vinylbutyrolactones by intramolecular oxaallylic alkylation with alcohols.

Project description:Gold(I)-N-heterocyclic carbene (NHC) complexes proved to be a reliable catalytic system for the direct synthesis of functionalized γ-vinylbutyrolactones by intramolecular oxaallylic alkylation with primary alcohols. Good isolated chemical yields were obtained for a range of malonyl and acetate derivatives. The good performance in reagent-grade solvents and the functional group/moisture tolerance make this catalytic process a promising route for the synthesis of architecturally complex polycyclic structures.

| S-EPMC3182428 | biostudies-literature

Gold(I)-catalyzed intramolecular hydroarylation of allenes.

Project description:Gold(I) complexes react with 4-allenyl arenes in an exo fashion to furnish vinyl-substituted benzocycles. Phosphite gold(I) monocations were found to be optimal, and the catalyst was tolerant of ethers, esters, and pyrroles. Reactions proceeded in unpurified solvent at room temperature.

| S-EPMC2924810 | biostudies-literature

Leveraging the micellar effect: gold-catalyzed dehydrative cyclizations in water at room temperature.

Project description:The first examples of gold-catalyzed cyclizations of diols and triols to the corresponding hetero- or spirocycles in an aqueous medium are presented. These reactions take place within nanomicelles, where the hydrophobic effect is operating, thereby driving the dehydrations, notwithstanding the surrounding water. By the addition of simple salts such as sodium chloride, reaction times and catalyst loadings can be significantly decreased.

| S-EPMC4219360 | biostudies-literature

Gold(I)-Catalyzed Desymmetrization of 1,4-Dienes by an Enantioselective Tandem Alkoxylation/Claisen Rearrangement.

Project description:An enantioselective alkoxylation/Claisen rearrangement reaction was achieved by a strategic desymmetrization of 1,4-dienes under the catalysis of (S)-DTBM-Segphos(AuCl)2/AgBF4. This reaction system was highly selective for the formation of 3,3-rearrangement products, providing cycloheptenes with various substitutions in good yield and good to excellent enantioselectivity. This transformation was further extended to bicyclic ring substrates, providing the opportunity to easily assemble 5,6- and 6,7-fused ring systems.

| S-EPMC4529066 | biostudies-literature

Gold-Catalyzed Intramolecular Cyclizations of Cyclopropenes with Propargylic Esters.

Project description:Homogeneous gold catalysts are interesting as they can act as potent carbophilic Lewis acids to activate the ? bonds of alkynes, allenes, and alkenes. Many impressive applications for the formation of C-C or C-heteroatom bonds have been found due to the excellent functional group compatibility of these catalysts and the air and moisture tolerance of their reactions. Here, we have developed gold-catalyzed novel intramolecular cycloisomerizations of nitrogen or oxygen-tethered cyclopropenes with propargylic esters. The reaction proceeded through different pathways according to different substituent styles, affording 5-azaspiro[2.5]oct-7-enes and bicyclo[4.1.0]heptanes.

| S-EPMC4906491 | biostudies-literature

Gold(I)-Catalyzed Enantioselective Intramolecular Hydroamination of Allenes with Ureas.

Project description:Enantioselective intramolecular hydroamination of N-allenyl ureas catalyzed by an enantiomerically enriched bis(gold) phosphine complex forms pyrrolidine derivatives in good yield with up to 93% ee.

| S-EPMC3169097 | biostudies-literature

Gold(I)-catalyzed intramolecular amination of allylic alcohols with alkylamines.

Project description:A 1:1 mixture of (1)AuCl [1 = P(t-Bu)(2)o-biphenyl] and AgSbF(6) catalyzes the intramolecular amination of allylic alcohols with alkylamines to form substituted pyrrolidine and piperidine derivatives. Gold(I)-catalyzed cyclization of (R,Z)-8-(N-benzylamino)-3-octen-2-ol (96% ee, 95% de) led to isolation of (R,E)-1-benzyl-2-(1-propenyl)piperidine in 99% yield with 96% ee, consistent with the net syn addition of the amine relative to the departing hydroxyl group.

| S-EPMC3429346 | biostudies-literature

Diastereoselective pyrrolidine synthesis via copper promoted intramolecular aminooxygenation of alkenes: formal synthesis of (+)-monomorine.

Project description:The diastereoselectivity of the copper-promoted intramolecular aminooxygenation of various alkene substrates was investigated. Alpha-substituted 4-pentenyl sulfonamides favor the formation of 2,5-cis-pyrrolidines (dr >20:1) giving excellent yields which range from 76-97% while gamma-substituted substrates favor the 2,3-trans pyrrolidine adducts with moderate selectivity (ca. 3:1). A substrate whose N-substituent was directly tethered to the alpha-carbon exclusively yielded the 2,5-trans pyrrolidine. The synthetic utility of the method was demonstrated by a short and efficient formal synthesis of (+)-monomorine.

| S-EPMC2714983 | biostudies-literature

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