Browse
Submit Data
Databases
API
Help

Dataset Information

34 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Wdowik T

PROVIDER: S-EPMC8293922 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

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(II)-catalyzed enantioselective intramolecular carboamination of alkenes.

Project description: Not available

| S-EPMC2531285 | 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

Diastereo- and enantioselective copper-catalyzed intramolecular carboamination of alkenes for the synthesis of hexahydro-1H-benz[f]indoles.

Project description:A new method for the enantioselective synthesis of hexahydro-1H-benz[f]indoles is described. This copper-catalyzed enantioselective intramolecular alkene carboamination process can install vicinal tertiary and quaternary carbon stereocenters with high levels of diastereo- and enantioselectivity. The C-C bond-forming component of the reaction constitutes a C-H functionalization and no electronic activation of the aryl ring that undergoes addition is required. A known 5-HT(1A) receptor antagonist was synthesized efficiently using this method.

| S-EPMC2966542 | biostudies-literature

Copper-catalyzed oxytrifluoromethylation of unactivated alkenes.

Project description:A mild, versatile, and convenient method for the efficient oxytrifluoromethylation of unactivated alkenes based on a copper-catalyzed oxidative difunctionalization strategy has been developed. This methodology provides access to a variety of classes of synthetically useful CF(3)-containing building blocks from simple starting materials.

| S-EPMC3419474 | biostudies-literature

Rhodium-catalyzed asymmetric intramolecular hydroamination of unactivated alkenes.

Project description: Not available

| S-EPMC3394429 | biostudies-literature

A computational study of the copper(II)-catalyzed enantioselective intramolecular aminooxygenation of alkenes.

Project description:The origin of the enantioselectivity in the [Cu(R,R)-Ph-box](OTf)2-catalyzed intramolecular aminooxygenation of N-sulfonyl-2-allylanilines and 4-pentenylsulfonamides to afford chiral indolines and pyrrolidines, respectively, was investigated using density functional theory (DFT) calculations. The pyrrolidine-forming transition-state model for the major enantiomer involves a chairlike seven-membered cyclization transition state with a distorted square-planar copper center, while the transition-state model for the minor enantiomer was found to have a boatlike cyclization geometry having a distorted tetrahedral geometry about the copper center. Similar copper-geometry trends were observed in the chiral indoline-forming reactions. These models were found to be qualitatively consistent with experimental results and allow for rationalization of how substitution on the substrate backbone and N-sulfonyl substituent affect the level of enantioselectivity in these and related copper(II)-catalyzed enantioselective reactions.

| S-EPMC3940240 | biostudies-literature

Copper-catalyzed diamination of unactivated alkenes with hydroxylamines.

Project description:A copper-catalyzed regio- and stereoselective diamination of unactivated alkenes has been developed with O-acylhydroxylamines as electrophilic nitrogen sources and oxidants. This method provides the first example of metal-catalyzed alkene diamination for directly installing an electron-rich amino group and extends the diamination scope for the synthesis of diverse 1,2-diamines. It offers a rapid and efficient approach to construct a wide range of 1,2-diamines that are an important structural motif in organic synthesis, medicines, catalysts and ligands.

| S-EPMC5707484 | 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

Intramolecular Pd-catalyzed carboetherification and carboamination. Influence of catalyst structure on reaction mechanism and product stereochemistry.

Project description:The intramolecular Pd-catalyzed carboetherification of alkenes affords 2-indan-1-yltetrahydrofuran products in moderate to good yield with good to excellent levels of diastereoselectivity. The stereochemical outcome of these reactions is dependent on the structure of the Pd catalyst. Use of PCy(3) or P[(4-MeO)C(6)H(4)](3) as the ligand for Pd leads to syn-addition of the arene and the oxygen atom across the double bond, whereas use of (+/-)-BINAP or DPP-benzene affords products that result from anti-addition. The catalyst-induced change in stereochemistry is likely due to a change in reaction mechanism. Evidence is presented that suggests the syn-addition products derive from an unprecedented transannular alkene insertion of an 11-membered Pd(Ar)(OR) complex. In contrast, the anti-addition products appear to arise from Wacker-type anti-oxypalladation. Studies on analogous Pd-catalyzed intramolecular carboamination reactions, which afford 2-indan-1-ylpyrrolidines that result from syn-addition, are also described.

| S-EPMC2710616 | 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