Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A catalytic enantioselective stereodivergent aldol reaction.

ABSTRACT: The aldol reaction is among the most powerful and strategically important carbon-carbon bond-forming transformations in organic chemistry. The importance of the aldol reaction in constructing chiral building blocks for complex small-molecule synthesis has spurred continuous efforts toward the development of direct catalytic variants. The realization of a general catalytic aldol reaction with control over both the relative and absolute configurations of the newly formed stereogenic centers has been a longstanding goal in the field. Here, we report a decarboxylative aldol reaction that provides access to all four possible stereoisomers of the aldol product in one step from identical reactants. The mild reaction can be carried out on a large scale in an open flask, and generates CO₂ as the only by-product. The method tolerates a broad substrate scope and generates chiral β-hydroxy thioester products with substantial downstream utility.

SUBMITTER: Rahman MA

PROVIDER: S-EPMC10017038 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A catalytic enantioselective stereodivergent aldol reaction.

Rahman Md Ataur MA Cellnik Torsten T Ahuja Brij Bhushan BB Li Liang L Healy Alan R AR

Science advances 20230315 11

The aldol reaction is among the most powerful and strategically important carbon-carbon bond-forming transformations in organic chemistry. The importance of the aldol reaction in constructing chiral building blocks for complex small-molecule synthesis has spurred continuous efforts toward the development of direct catalytic variants. The realization of a general catalytic aldol reaction with control over both the relative and absolute configurations of the newly formed stereogenic centers has be ...[more]

PMID: 36921040

Similar Datasets

Catalytic enantioselective O-nitrosocarbonyl aldol reaction of β-dicarbonyl compounds.

Project description:The first example of a Cu-catalyzed asymmetric O-nitrosocarbonyl aldol reaction is described. This novel protocol allows convenient access to highly enantioenriched α-hydroxy-β-ketoesters including the antibacterial natural product kjellmanianone (up to 99% ee). MnO(2) was introduced as a mild efficient oxidant for the in situ generation of nitrosocarbonyl species from hydroxamic acid derivatives.

| S-EPMC3515642 | biostudies-literature

An Enantioselective Decarboxylative Glycolate Aldol Reaction.

Project description:Herein, we report the application of a benzyloxy-functionalized malonic acid half thioester as an activated ester equivalent in a highly enantioselective decarboxylative glycolate aldol reaction. This robust method operates at ambient temperature, tolerates air and moisture, and generates CO2 as the only byproduct. The synthetic applicability of the method is demonstrated by the large-scale enantiodivergent synthesis of α-benzyloxy-β-hydroxybutyric acid thioester and its subsequent conversion to diverse polyoxygenated building blocks, deoxy-sugars, and (-)-angiopterlactone B.

| S-EPMC11519920 | biostudies-literature

Hydrogen bond catalyzed enantioselective vinylogous Mukaiyama aldol reaction.

Project description:[chemical reaction: see text]. The concept of hydrogen bonding catalysis was extended to the vinylogous Mukaiyama aldol reaction, which gives rapid access to polyketide derivatives. The reaction of the silyldienol ether shown and a range of aldehydes catalyzed by TADDOL proceeds regiospecifically to produce the addition products in good yields and enantiomeric excesses.

| S-EPMC2537470 | biostudies-literature

A catalytic asymmetric vinylogous Mukaiyama aldol reaction.

Project description:A vinylogous Mukaiyama aldol reaction, conducted using 10 mol % of a BITIP catalyst and B(OMe)3 as an additive, effects an enantioselective four-carbon chain extension to give versatile E-alpha,beta-unsaturated thiol esters.

| S-EPMC2516376 | biostudies-literature

Organocatalyzed enantioselective aldol reaction of 1H-pyrrole-2,3-diones.

Project description:The enantioselective cross aldol reaction of 1-benzyl 4,5-dioxo-2-aryl-4,5-dihydro-1H-pyrrole-3-carboxylates and ketones was studied with proline derivatives or cinchona alkaloid-derived primary amines as the catalysts for the first time. trans-4-Benzoyloxy-L-proline (15) was found to be the best catalyst for acyclic ketones. For cyclohexanone, the best results were achieved with 9-deoxy-9-epi-aminoquinine (18) as the catalyst in the presence of racemic 1,1'-binaphthyl-2,2'-diyl hydrogen phosphate (19) as the cocatalyst. Using these protocols, 3-alkyl-3-hydroxy-1H-pyrrol-2(3H)-one derivatives were obtained in excellent yields and good to high ee values (up to 94% ee).

| S-EPMC3335438 | biostudies-literature

Catalytic Diastereo- and Enantioselective Synthesis of Tertiary Trifluoromethyl Carbinols through a Vinylogous Aldol Reaction of Alkylidenepyrazolones with Trifluoromethyl Ketones.

Project description:A diastereo- and enantioselective organocatalytic aldol reaction between alkylidenepyrazolones and trifluoromethyl ketones leading to chiral tertiary alcohols bearing a trifluoromethyl group is presented. The methodology is based on the use of a bifunctional organocatalyst in order to activate the γ-hydrogen atoms of the alkylidenepyrazolone nucleophile and the carbonyl group of the trifluoromethylarylketone providing highly functionalized trifluoromethyl alcohols with moderate yields, excellent diastereoselectivity, and moderate to good enantioselectivity. Experiments monitoring the conversion by 1H NMR and the enantiomeric excess by HPLC with the reaction time showed that full conversion of the starting materials is not achieved and that the enantiomeric excess decreases upon extended times, probably due to the reversibility of the reaction.

| S-EPMC8981347 | biostudies-literature

Enantioselective synthesis of (-)-chloramphenicol via silver-catalysed asymmetric isocyanoacetate aldol reaction.

Project description:The highly enantio- and diastereoselective aldol reaction of isocyanoacetates catalysed by Ag2O and cinchona-derived amino phosphines applied to the synthesis of (-)- and (+)-chloramphenicol is described. The concise synthesis showcases the utility of this catalytic asymmetric methodology for the preparation of bioactive compounds possessing α-amino-β-hydroxy motifs.

| S-EPMC4756631 | biostudies-literature

Stereodivergent assembly of tetrahydro-γ-carbolines via synergistic catalytic asymmetric cascade reaction.

Project description:Enantiomerically enriched indole-containing heterocycles play a vital role in bioscience, medicine, and chemistry. As one of the most attractive subtypes of indole alkaloids, highly substituted tetrahydro-γ-carbolines are the basic structural unit in many natural products and pharmaceuticals. However, the syntheses of tetrahydro-γ-carbolines with high functionalities from readily available reagents are significant challenging. In particular, the stereodivergent syntheses of tetrahydro-γ-carbolines containing multi-stereogenic centers remain quite difficult. Herein, we report an expedient and stereodivergent assembly of tetrahydro-γ-carbolines with remarkably high levels of stereoselective control in an efficient cascade process from aldimine esters and indolyl allylic carbonates via a synergistic Cu/Ir catalyst system. Control experiments-guided optimization of synergistic catalysts and mechanistic investigations reveal that a stereodivergent allylation reaction and a subsequent highly stereoselective iso-Pictet-Spengler cyclization are the key elements to success.

| S-EPMC6895234 | biostudies-literature

Dinuclear zinc-ProPhenol-catalyzed enantioselective α-hydroxyacetate aldol reaction with activated ester equivalents.

Project description:An enantioselective α-hydroxyacetate aldol reaction that employs N-acetyl pyrroles as activated ester equivalents and generates syn 1,2-diols in good yield and diastereoselectivity is reported. This dinuclear zinc-ProPhenol-catalyzed transformation proceeds with high enantioselectivity with a wide variety of substrates including aryl, alyl, and alkenyl aldehydes. The resulting α,β-dihydroxy activated esters are versatile intermediates for the synthesis of a variety of carboxylic acid derivatives including amides, esters, and unsymmetrical ketones.

| S-EPMC3812954 | biostudies-literature

A general diastereoselective catalytic vinylogous aldol reaction among tetramic acid-derived pyrroles.

Project description:A catalytic diastereoselective aldol reaction has been developed for N1-arylated/C2-O-silylated/C3-methylated and brominated/C4-O-methylated pyrroles in its reactions with various aldehydes. Syn adducts emerge with regard to the vicinal nitrogen and oxygen heteroatom substituents. The N1-aryl residue undergoes oxidative cleavage, and the C3-bromine atom undergoes palladium-mediated coupling reactions, both without disturbing the newly created stereocenters.

| S-EPMC4156244 | 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