Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copper-Catalyzed Enantioselective Oxysulfenylation of Alkenols: Synthesis of Arylthiomethyl-Substituted Cyclic Ethers.

ABSTRACT: Saturated heterocycles containing oxygen and sulfur are found in biologically significant molecules. The enantioselective oxysulfenylation of alkenols provides a straightforward synthesis route. To date, organocatalytic methods have dominated this approach. Herein, a complementary approach via copper catalysis is presented. This exoselective method provides enantioenriched arylthiomethyl-substituted tetrahydrofurans, phthalans, isochromans, and morpholines from acyclic alkenols. This method provides the largest scope to date for the exocyclization mode, and with generally high enantioselectivity. The enantioselectivity of this copper-catalyzed oxysulfenylation is rationalized by a proposed mechanism involving alkene oxycupration followed by C─S bond formation via radical-mediated atom transfer.

SUBMITTER: Burde AS

PROVIDER: S-EPMC10022821 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Copper-Catalyzed Enantioselective Oxysulfenylation of Alkenols: Synthesis of Arylthiomethyl-Substituted Cyclic Ethers.

Burde Ameya S AS Chemler Sherry R SR

ACS catalysis 20220613 13

Saturated heterocycles containing oxygen and sulfur are found in biologically significant molecules. The enantioselective oxysulfenylation of alkenols provides a straightforward synthesis route. To date, organocatalytic methods have dominated this approach. Herein, a complementary approach via copper catalysis is presented. This exoselective method provides enantioenriched arylthiomethyl-substituted tetrahydrofurans, phthalans, isochromans, and morpholines from acyclic alkenols. This method prov ...[more]

PMID: 36937986

Similar Datasets

Copper-Catalyzed Enantioselective Hydroalkoxylation of Alkenols for the Synthesis of Cyclic Ethers.

Project description:The copper-catalyzed enantioselective intramolecular hydroalkoxylation of unactivated alkenes for the synthesis of tetrahydrofurans, phthalans, isochromans, and morpholines from 4- and 5-alkenols is reported. The substrate scope is complementary to existing enantioselective alkene hydroalkoxylations and is broad with respect to substrate backbone and alkene substitution. The asymmetric induction and isotopic labeling studies support a polar/radical mechanism involving enantioselective oxycupration followed by C-[Cu] homolysis and hydrogen atom transfer. Synthesis of the antifungal insecticide furametpyr was accomplished.

| S-EPMC7541751 | biostudies-literature

Synthesis of Spirocyclic Ethers by Enantioselective Copper-Catalyzed Carboetherification of Alkenols.

Project description:Spirocyclic ethers can be found in bioactive compounds. This copper-catalyzed enantioselective alkene carboetherification provides 5,5-, 5,6- and 6,6-spirocyclic products containing fully substituted chiral carbon centers with up to 99 % enantiomeric excess. This reaction features the formation of two rings from acyclic substrates, 1,1-disubstituted alkenols functionalized with either arenes, alkenes, or alkynes, and clearly constitutes a powerful way to synthesize chiral spirocyclic ethers.

| S-EPMC6375082 | biostudies-literature

Copper-catalyzed enantioselective alkene carboetherification for the synthesis of saturated six-membered cyclic ethers.

Project description:The enantioselective copper-catalyzed oxidative coupling of alkenols with styrenes for the construction of dihydropyrans, isochromans, pyrans and morpholines is reported. A concise formal synthesis of a σ1 receptor ligand using this alkene carboetherification methodology was demonstrated. Ligand, solvent and base all impact reaction efficiency. DFT transition state calculations are presented.

| S-EPMC8590114 | biostudies-literature

Copper-catalyzed enantioselective synthesis of bridged bicyclic ketals from 1,1-disubstituted-4-methylene-1,6-hexanediols and related alkenols.

Project description:Bridged bicyclic ketals display a range of bioactivities. Their catalytic enantioselective synthesis from acyclic 1,1-disubstituted alkene diols is disclosed. This reaction combines asymmetric catalysis with a distal radical migration. Alkynes and arenes undergo the group transfer.

| S-EPMC8018521 | biostudies-literature

Enantioselective Copper-Catalyzed Synthesis of Trifluoromethyl-Cyclopropylboronates.

Project description:A copper-catalyzed enantioselective cyclopropanation involving trifluorodiazoethane in the presence of alkenyl boronates has been developed. This transformation enables the preparation of 2-substituted-3-(trifluoromethyl)cyclopropylboronates with high levels of stereocontrol. The products are valuable synthetic intermediates by transformation of the boronate group. This methodology can be applied to the synthesis of novel trifluoromethylated analogues of trans-2-arylcyclopropylamines, which are prevalent motifs in biologically active compounds.

| S-EPMC8895459 | biostudies-literature

Ru-catalyzed sequence for the synthesis of cyclic amido-ethers.

Project description:Efficient synthesis of versatile building blocks for enabling medicinal chemistry research has always challenged synthetic chemists to develop innovative methods. Of particular interest are the methods that are amenable to the synthesis of chemically distinct and diverse classes of pharmaceutically relevant motifs. Herein we report a general method for the one-pot synthesis of cyclic α-amido-ethers containing different amide functionalities including lactams, tetramic acids and amino acids. For the incorporation of the nucleotide bases, a chemo and regioselective palladium-catalyzed transformation has been developed, providing rapid access to nucleoside analogs.

| S-EPMC5299796 | biostudies-literature

Copper-Catalyzed Regio- and Enantioselective Hydroboration of Difluoroalkyl-Substituted Internal Alkenes.

Project description:Catalytic asymmetric hydroboration of fluoroalkyl-substituted alkenes is a straightforward approach to access chiral small molecules possessing both fluorine and boron atoms. However, enantioselective hydroboration of fluoroalkyl-substituted alkenes without fluorine elimination has been a long-standing challenge in this field. Herein, a copper-catalyzed hydroboration of difluoroalkyl-substituted internal alkenes with high levels of regio- and enantioselectivities is reported. The native carbonyl directing group, copper hydride system, and bisphosphine ligand play crucial roles in suppressing the undesired fluoride elimination. This atom-economic protocol provides a practical synthetic platform to obtain a wide scope of enantioenriched secondary boronates bearing the difluoromethylene moieties under mild conditions. Synthetic applications including functionalization of biorelevant molecules, versatile functional group interconversions, and preparation of difluoroalkylated Terfenadine derivative are also demonstrated.

| S-EPMC10724385 | biostudies-literature

Chiral imine copper chloride-catalyzed enantioselective desymmetrization of 2-substituted 1,2,3-propanetriols.

Project description:Catalytic enantioselective desymmetrization of meso-2-substituted glycerols has been developed to secure a novel synthetic route to chiral tertiary alcohols. The transformation has been realized by monobenzoylation using benzoyl chloride and triethylamine in the presence of the imine ligand (25)-CuCl2 complex in THF at ambient temperature. The desymmetrization turned out to be greatly dependent on acylating reagent, base, solvent, and needless to say, catalyst. Extensive screening of chiral ligands led us to combine bromopyridinecarboxaldehyde 1 and phenyloxazoline amine 12 derived from tert-leucine, the bromo and phenyl substituents of which proved to be indispensable. All of the substrates have been desymmetrized to the corresponding monobenzoates with high enantioselectivity up to 96% enantiomeric excess. The catalytic system allows broad structural diversity of substrates and its synthetic versatility has been demonstrated by an efficient synthetic route to a known key precursor 68 of triazole antifungals.

| S-EPMC1785247 | biostudies-literature

Trapping Hemiacetals with Phosphono Substituted Palladium π-Allyl Complexes for the Synthesis of Substituted Cyclic Ethers.

Project description:Oxidation of hydroxy substituted phosphono allylic carbonates gave the aldehyde substituted phosphonates in good yield. Stereospecific palladium (0)-catalyzed cyclization in the presence of methanol or water gave acetal tetrahydrofuran and tetrahydropyran vinyl phosphonate products derived from hemiacetal trapping. The tetrahydrofuran acetals undergo Lewis acid catalyzed addition of nucleophiles to give diastereoisomeric mixtures of substituted tetrahydrofurans.

| S-EPMC4518476 | biostudies-literature

Copper-Catalyzed Synthesis of Hindered Ethers from α-Bromo Carbonyl Compounds.

Project description:A catalytic method for the synthesis of sterically hindered ethers and thioethers from α-bromo carbonyl compounds and the corresponding nucleophiles using an inexpensive Cu(I) catalytic system is reported. This facile transformation takes place at ambient temperature and does not require the exclusion of air or moisture; thus, it is well-suited for the functionalization and derivatization of complex organic molecules.

| S-EPMC7802898 | 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