Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Enantioselective Addition of Dialkyl Malonates to β-Arylethenesulfonyl Fluorides under High-Pressure Conditions.

ABSTRACT: Application of high-pressure conditions enables enantioselective Michael-type addition of dialkyl malonates to β-arylethenesulfonyl fluorides. The reaction is efficiently catalyzed with 5 mol % of tertiary amino-thiourea at 9 kbar. Chiral alkanesulfonyl fluorides are formed in yields of up to 96% and enantioselectivities of up to 92%. Functionalization of the adducts via sulfur fluoride exchange (SuFEx) reaction and desulfonylative cyclization is demonstrated.

SUBMITTER: Kopyt M

PROVIDER: S-EPMC10521026 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Enantioselective Addition of Dialkyl Malonates to β-Arylethenesulfonyl Fluorides under High-Pressure Conditions.

Kopyt Michał M Tryniszewski Michał M Barbasiewicz Michał M Kwiatkowski Piotr P

Organic letters 20230901 37

Application of high-pressure conditions enables enantioselective Michael-type addition of dialkyl malonates to β-arylethenesulfonyl fluorides. The reaction is efficiently catalyzed with 5 mol % of tertiary amino-thiourea at 9 kbar. Chiral alkanesulfonyl fluorides are formed in yields of up to 96% and enantioselectivities of up to 92%. Functionalization of the adducts via sulfur fluoride exchange (SuFEx) reaction and desulfonylative cyclization is demonstrated. ...[more]

PMID: 37655810

Similar Datasets

Enantioselective Organocatalytic Conjugate Addition of Malonates to β,β-Disubstituted β-Trifluoromethyl Enones under High Pressure.

Project description:The first enantioselective Michael addition of malonates to acyclic β,β-disubstituted enones has been developed. Sterically hindered β-trifluoromethyl α,β-unsaturated 2-acyl thiazoles and benzothiazoles were found to be the most reactive groups of enones in the reaction catalyzed by bifunctional tertiary amine-thioureas (2-5 mol %). However, application of hyperbaric conditions (8-10 kbar) was required. The adducts containing quaternary stereogenic centers with a CF3 group were obtained in high yields (vs <1% at 1 bar) with enantiomeric excesses up to 95%.

| S-EPMC11894651 | biostudies-literature

Isothiourea-Catalyzed Enantioselective Michael Addition of Malonates to α,β-Unsaturated Aryl Esters.

Project description:An enantioselective Michael addition of malonates to α,β-unsaturated para-nitrophenyl esters was achieved using the Lewis basic isothiourea HyperBTM, giving excellent levels of product enantioselectivity (up to >99:1 enantiomeric ratio) in good yields and with complete regioselectivity (>20:1 regioselectivity ratio) in the presence of alternative (phenyl ketone and ethyl ester) Michael acceptors. Density functional theory calculations indicate that N-acylation is rate-limiting. This constitutes a rare example of a highly enantioselective addition of simple, readily available malonates to α,β-unsaturated esters.

| S-EPMC9278409 | biostudies-literature

Enantioselective Michael addition of malonates to α,β-unsaturated ketones catalyzed by 1,2-diphenylethanediamine.

Project description:A general and highly enantioselective Michael addition of malonates to cinnamones and chalcones has been developed. The commercially available 1,2-diphenylethanediamine could be directly utilized as the organocatalyst to furnish the desired adducts in satisfactory yield (61-99%) and moderate to excellent enantiopurity (65 to >99% ee). β-Ketoester was also a competent donor and was employed to construct densely functionalized cyclohexenones via a tandem Michael-aldol condensation process.

| S-EPMC9091971 | biostudies-literature

Enzymatic enantioselective decarboxylative protonation of heteroaryl malonates.

Project description:The enzyme aryl/alkenyl malonate decarboxylase (AMDase) catalyses the enantioselective decarboxylative protonation (EDP) of a range of disubstituted malonic acids to give homochiral carboxylic acids that are valuable synthetic intermediates. AMDase exhibits a number of advantages over the non-enzymatic EDP methods developed to date including higher enantioselectivity and more environmentally benign reaction conditions. In this report, AMDase and engineered variants have been used to produce a range of enantioenriched heteroaromatic α-hydroxycarboxylic acids, including pharmaceutical precursors, from readily accessible α-hydroxymalonates. The enzymatic method described here represents an improvement upon existing synthetic chemistry methods that have been used to produce similar compounds. The relationship between the structural features of these new substrates and the kinetics associated with their enzymatic decarboxylation is explored, which offers further insight into the mechanism of AMDase.

| S-EPMC4517146 | biostudies-literature

Highly Enantioselective Lewis Acid Catalyzed Conjugate Addition of Imidazo[1,2-<i>a</i>]pyridines to α,β-Unsaturated 2-Acylimidazoles under Mild Conditions.

Project description:A highly enantioselective protocol for the conjugate addition of 2-arylimidazo[1,2-a]pyridines and other imidazo derivatives to α,β-unsaturated 2-acylimidazoles is described. The method uses a previously reported chiral-at-metal rhodium catalyst and provides the corresponding adducts in yields of 25-98% with enantioselectivities up to er > 99:1. Additionally, the transformation proceeds under mild conditions using ethanol as the solvent at room temperature.

| S-EPMC11197092 | biostudies-literature

Asymmetric Michael Addition Organocatalyzed by α,β-Dipeptides under Solvent-Free Reaction Conditions.

Project description:The application of six novel α,β-dipeptides as chiral organocatalysts in the asymmetric Michael addition reaction between enolizable aldehydes and N-arylmaleimides or nitroolefins is described. With N-arylmaleimides as substrates, the best results were achieved with dipeptide 2 as a catalyst in the presence of aq. NaOH. Whereas dipeptides 4 and 6 in conjunction with 4-dimethylaminopyridine (DMAP) and thiourea as a hydrogen bond donor proved to be highly efficient organocatalytic systems in the enantioselective reaction between isobutyraldehyde and various nitroolefins.

| S-EPMC6152315 | biostudies-literature

Nickel-Catalyzed Decarbonylative Stannylation of Acyl Fluorides under Ligand-Free Conditions.

Project description:Nickel-catalyzed decarbonylative stannylation of acyl fluorides under ligand-free conditions was disclosed. A variety of aromatic acyl fluorides are capable of reacting with silylstannanes in the presence of cesium fluoride. A one-pot decarbonylative stannylation/Migita-Kosugi-Stille reaction of benzoyl fluoride, giving rise to the direct formation of the corresponding cross-coupled products, further demonstrated the synthetic utility of the present method. This newly developed methodology with a good functional-group compatibility via C-F bond cleavage and C-Sn bond formation under nickel catalysis opens a new area for the functionalization of acyl fluorides in terms of carbon-heteroatom bond formation.

| S-EPMC6539589 | biostudies-literature

Ultrasound-Assisted Green Synthesis of Dialkyl Peroxides under Phase-Transfer Catalysis Conditions.

Project description:The dialkyl peroxides, which contain a thermally unstable oxygen-oxygen bond, are an important source of radical initiators and cross-linking agents. New efficient and green methods for their synthesis are still being sought. Herein, ultrasound-assisted synthesis of dialkyl peroxides from alkyl hydroperoxides and alkyl bromides in the presence of an aqueous solution of an inorganic base was systematically studied under phase-transfer catalysis (PTC) conditions. The process run in a tri-liquid system in which polyethylene glycol as a phase-transfer catalyst formed a third liquid phase between the organic and inorganic phases. The use of ultrasound provided high yields of organic peroxides (70-99%) in significantly shorter reaction times (1.5 h) in comparison to reaction with magnetic stirring (5.0 h). In turn, conducting the reaction in the tri-liquid PTC system allowed easy separation of the catalyst and its multiple use without significant loss of activity.

| S-EPMC6982749 | biostudies-literature

Organocatalytic asymmetric addition of malonates to unsaturated 1,4-diketones.

Project description:The organocatalytic Michael addition of malonates to symmetric unsaturated 1,4-diketones catalyzed by thiourea and squaramide derivatives with Cinchona alkaloids afforded the formation of a new C-C bond in high yields (up to 98%) and enantiomeric purities (up to 93%). The absolute configuration of the product was suggested from comparison of the experimental and calculated VCD spectra of the reaction product 3a.

| S-EPMC3458770 | biostudies-literature

Decomposition and oligomerization of 2,3-naphthyridine under high-pressure and high-temperature conditions.

Project description:The chemical reaction of 2,3-naphthyridine, a nitrogen-containing aromatic compound, was investigated at pressures ranging from 0.5 to 1.5 GPa and temperatures from 473 to 573 K. A distinct decrease in the amount of residual 2,3-naphthyridine was observed in the samples recovered after reaction at ˃523 K at 0.5 and 1.0 GPa, and ˃548 K at 1.5 GPa. The formation of o-xylene and o-tolunitrile accompanied a decreasing N/C ratio of the reaction products, indicating decomposition of the aromatic ring and release of nitrogen. Precise analysis of the reaction products indicated the oligomerization of decomposed products with the residual 2,3-naphthyridine to form larger molecules up to 7mers. Nitrogen in the aromatic ring accelerated reactions to decompose the molecule and to oligomerize at lower temperatures than those typically reported for aromatic hydrocarbon oligomerization. The major reaction mechanism was similar between 0.5 and 1.5 GPa, although larger products preferentially formed in the samples at higher pressure.

| S-EPMC6517384 | 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