Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Versatile Enantioselective Synthesis of Functionalized Lactones via Copper-Catalyzed Radical Oxyfunctionalization of Alkenes.

ABSTRACT: A versatile method for the rapid synthesis of diverse enantiomerically enriched lactones has been developed based on Cu-catalyzed enantioselective radical oxyfunctionalization of alkenes. The scope of this strategy encompasses a series of enantioselective difunctionalization reactions: oxyazidation, oxysulfonylation, oxyarylation, diacyloxylation, and oxyalkylation. These reactions provide straightforward access to a wide range of useful chiral lactone building blocks containing tetrasubstituted stereogenic centers, which are hard to access traditionally.

SUBMITTER: Zhu R

PROVIDER: S-EPMC4490856 | biostudies-other | 2015 Jul

REPOSITORIES: biostudies-other

ACCESS DATA

Json Xml

Publications

Versatile Enantioselective Synthesis of Functionalized Lactones via Copper-Catalyzed Radical Oxyfunctionalization of Alkenes.

Zhu Rong R Buchwald Stephen L SL

Journal of the American Chemical Society 20150623 25

A versatile method for the rapid synthesis of diverse enantiomerically enriched lactones has been developed based on Cu-catalyzed enantioselective radical oxyfunctionalization of alkenes. The scope of this strategy encompasses a series of enantioselective difunctionalization reactions: oxyazidation, oxysulfonylation, oxyarylation, diacyloxylation, and oxyalkylation. These reactions provide straightforward access to a wide range of useful chiral lactone building blocks containing tetrasubstituted ...[more]

PMID: 26070105

Similar Datasets

Copper-catalyzed carbo-difluoromethylation of alkenes via radical relay.

Project description:Organic molecules that contain alkyl-difluoromethyl moieties have received increased attention in medicinal chemistry, but their synthesis in a modular and late-stage fashion remains challenging. We report herein an efficient copper-catalyzed radical relay approach for the carbo-difluoromethylation of alkenes. This approach simultaneously introduces CF2H groups along with complex alkyl or aryl groups into alkenes with regioselectivity opposite to traditional CF2H radical addition. We demonstrate a broad substrate scope and a wide functional group compatibility. This scalable protocol is applied to the late-stage functionalization of complex molecules and the synthesis of CF2H analogues of bioactive molecules. Mechanistic studies and density functional theory calculations suggest a unique ligand effect on the reactivity of the Cu-CF2H species.

| S-EPMC8169770 | biostudies-literature

Copper-catalyzed enantioselective arylalkynylation of alkenes.

Project description:A copper-catalyzed enantioselective arylalkynylation of alkenes with diaryliodonium salt and a monosubstituted alkyne is reported. The three-component coupling reactions proceed under mild reaction conditions with a broad substrate scope, leading to synthetically valuable 1,2-diaryl-3-butynes. The key to the success of this chemistry is the employment of the chiral bisoxazoline-phenylaniline (BOPA) ligand. A novel reaction pathway involving the phenyl radical generation under thermal copper catalysis is proposed according to mechanistic studies.

| S-EPMC7069229 | biostudies-literature

Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

Project description:Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of ?-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step.

| S-EPMC4097818 | biostudies-literature

Copper catalyzed enantioselective intramolecular aminooxygenation of alkenes.

Project description:The copper-catalyzed enantioselective intramolecular aminooxygenation of alkenes is reported herein. This is the first report of an enantioselective intramolecular alkene aminooxygenation process. N-Arylsulfonyl-2-allylanilines and 4-pentenylarylsulfonamides cyclize in high yield and with good enantioselectivity, providing new chiral methyleneoxy-functionalized dihydroindolines and pyrrolidines. Tetramethylaminopyridyl radical (TEMPO) serves as both the source of the oxygen and the stoichiometric oxidant. These reactions are catalyzed by copper(II) triflate, complexed with (4S,5R)-Bis-Phbox. The unprotected aminoalcohols can be obtained by sequential dissolving metal reductions of the N-S and O-N bonds.

| S-EPMC2674573 | biostudies-literature

Copper(II)-catalyzed enantioselective intramolecular carboamination of alkenes.

Project description: Not available

| S-EPMC2531285 | biostudies-literature

Enantioselective cyanation of benzylic C-H bonds via copper-catalyzed radical relay.

Project description:Direct methods for stereoselective functionalization of sp3-hybridized carbon-hydrogen [C(sp3)-H] bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C-H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp3)-CN bond formation upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90 to 99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C-H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways.

| S-EPMC5488708 | biostudies-literature

Stereoselective Synthesis of Trisubstituted Alkenes via Copper Hydride-Catalyzed Alkyne Hydroalkylation.

Project description:Alkenes are ubiquitous in organic chemistry, yet many classes of alkenes remain challenging to access by current synthetic methodology. Herein, we report a copper hydride-catalyzed approach for the synthesis of Z-configured trisubstituted alkenes with high stereo- and regioselectivity via alkyne hydroalkylation. A DTBM-dppf-supported Cu catalyst was found to be optimal, providing a substantial increase in product yield compared to reactions conducted with dppf as the ligand. DFT calculations show that the DTBM substitution leads to the acceleration of alkyne hydrocupration through combined ground and transition state effects related to preventing catalyst dimerization and enhancing catalyst-substrate dispersion interactions, respectively. Alkyne hydroalkylation was successfully demonstrated with methyl and larger alkyl tosylate electrophiles to produce a variety of (hetero)aryl-substituted alkenes in moderate to high yields with complete selectivity for the Z stereochemically configured products. In the formation of the key C-C bond, computational studies revealed a direct SN2 pathway for alkylation of the vinylcopper intermediate with in situ-formed alkyl iodides.

| S-EPMC10569085 | biostudies-literature

Chiral Indoline Synthesis Via Enantioselective Intramolecular Copper-Catalyzed Alkene Hydroamination.

Project description:An enantioselective copper-catalyzed hydroamination / cyclization of N-sulfonyl-2-allylanilines for the synthesis of chiral 2-methylindolines is reported. Chiral 2-methylindolines are important subunits in drugs and bioactive compounds. This method provides chiral N-sulfonyl-2-methyl indolines in up to 90% ee.

| S-EPMC3519432 | biostudies-literature

Enantioselective, Aerobic Copper-Catalyzed Intramolecular Carboamination and Carboetherification of Unactivated Alkenes.

Project description:Reduction of waste is an important goal of modern organic synthesis. We report herein oxidase reactivity for enantioselective intramolecular copper-catalyzed alkene carboamination and carboetherification reactions where previously used stoichiometric MnO2 has been replaced with oxygen. This substitution was risky as the reaction mechanism is thought to involve C-C bond formation via addition of alkyl carbon radicals to arenes. Such intermediates are also susceptible to C-O bond formation via O2 addition. Control of absolute stereochemistry under aerobic conditions was also uncertain. The oxidative cyclization efficiencies appear to track with the ease of the radical addition to the arenes.

| S-EPMC8293922 | 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

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