Browse
Submit Data
Databases
API
Help

Dataset Information

15 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Oxygenase-catalyzed desymmetrization of N,N-dialkyl-piperidine-4-carboxylic acids.

ABSTRACT: ?-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl piperidine-4-carboxylates to give products with two or three stereogenic centers.

SUBMITTER: Rydzik AM

PROVIDER: S-EPMC4497603 | biostudies-literature | 2014 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Oxygenase-catalyzed desymmetrization of N,N-dialkyl-piperidine-4-carboxylic acids.

Rydzik Anna M AM Leung Ivanhoe K H IK Kochan Grazyna T GT McDonough Michael A MA Claridge Timothy D W TD Schofield Christopher J CJ

Angewandte Chemie (International ed. in English) 20140827 41

γ-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl piperidine-4-carboxylates to give products with two or three stereogenic centers. ...[more]

PMID: 25164544

Similar Datasets

Nickel-Catalyzed Synthesis of Dialkyl Ketones from the Coupling of N-Alkyl Pyridinium Salts with Activated Carboxylic Acids.

Project description:While ketones are among the most versatile functional groups, their synthesis remains reliant upon reactive and low-abundance starting materials. In contrast, amide formation is the most-used bond-construction method in medicinal chemistry because the chemistry is reliable and draws upon large and diverse substrate pools. A new method for the synthesis of ketones is presented here that draws from the same substrates used for amide bond synthesis: amines and carboxylic acids. A nickel terpyridine catalyst couples N-alkyl pyridinium salts with in situ formed carboxylic acid fluorides or 2-pyridyl esters under reducing conditions (Mn metal). The reaction has a broad scope, as demonstrated by the synthesis of 35 different ketones bearing a wide variety of functional groups with an average yield of 60±16 %. This approach is capable of coupling diverse substrates, including pharmaceutical intermediates, to rapidly form complex ketones.

| S-EPMC7397811 | biostudies-literature

Direct Use of Carboxylic Acids in the Photocatalytic Hydroacylation of Styrenes To Generate Dialkyl Ketones.

Project description:A general protocol for the hydroacylation of styrenes from aliphatic carboxylic acids is reported. These reactions proceed via ?-scission of a phosphoranyl radical that is accessed by photoredox catalysis, followed by addition of the resulting acyl radical to the styrenyl olefin. We show that phosphine tunability is critical for efficient intermolecular coupling due to competitive quenching of the photocatalyst by the olefin. Primary, secondary, and structurally rigid tertiary carboxylic acids all generate valuable unsymmetrical dialkyl ketones.

| S-EPMC6927213 | biostudies-literature

Nickel-Catalyzed Conversion of Amides to Carboxylic Acids.

Project description:We report the conversion of amides to carboxylic acids using nonprecious metal catalysis. The methodology strategically employs a nickel-catalyzed esterification using 2-(trimethylsilyl)ethanol, followed by a fluoride-mediated deprotection in a single-pot operation. This approach circumvents catalyst poisoning observed in attempts to directly hydrolyze amides using nickel catalysis. The selectivity and mildness of this transformation are shown through competition experiments and the net-hydrolysis of a complex valine-derived substrate. This strategy addresses a limitation in the field with regard to functional groups accessible from amides using transition metal-catalyzed C-N bond activation and should prove useful in synthetic applications.

| S-EPMC7184625 | biostudies-literature

Biomimetic Desymmetrization of a Carboxylic Acid.

Project description:The enantioselective desymmetrization of carboxylic acids by chiral Brønsted base catalysis is reported, leading to bridged bicyclic lactones with up to 94% ee. Crystallographic analysis of a substrate-catalyst complex suggests an origin of stereocontrol, reminiscent of functional Brønsted bases in biological settings, and enabled reaction optimization. The products contain an all-carbon quaternary stereocenter and can be derivatized to functionalized cyclopentanes.

| S-EPMC5814305 | biostudies-literature

Cobalt-catalyzed highly enantioselective hydrogenation of ?,?-unsaturated carboxylic acids.

Project description:Asymmetric hydrogenation of ?,?-unsaturated acids catalyzed by noble metals has been well established, whereas, the asymmetric hydrogenation with earth-abundant-metal was rarely reported. Here, we describe a cobalt-catalyzed asymmetric hydrogenation of ?,?-unsaturated carboxylic acids. By using chiral cobalt catalyst bearing electron-donating diphosphine ligand, high activity (up to 1860 TON) and excellent enantioselectivity (up to >99% ee) are observed. Furthermore, the cobalt-catalyzed asymmetric hydrogenation is successfully applied to a broad spectrum of ?,?-unsaturated carboxylic acids, such as various ?-aryl and ?-alkyl cinnamic acid derivatives, ?-oxy-functionalized ?,?-unsaturated acids, ?-substituted acrylic acids and heterocyclic ?,?-unsaturated acids (30 examples). The synthetic utility of the protocol is highlighted by the synthesis of key intermediates for chiral drugs (6 cases). Preliminary mechanistic studies reveal that the carboxy group may be involved in the control of the reactivity and enantioselectivity through an interaction with the metal centre.

| S-EPMC7319995 | biostudies-literature

CuH-Catalyzed Asymmetric Reduction of ?,?-Unsaturated Carboxylic Acids to ?-Chiral Aldehydes.

Project description:The copper hydride (CuH)-catalyzed enantioselective reduction of ?,?-unsaturated carboxylic acids to saturated aldehydes is reported. This protocol provides a new method to access a variety of ?-chiral aldehydes in good yields, with high levels of enantioselectivity and broad functional group tolerance. A reaction pathway involving a ketene intermediate is proposed based on preliminary mechanistic studies and density functional theory calculations.

| S-EPMC5800953 | biostudies-literature

CuH-Catalyzed Asymmetric Reductive Amidation of α,β-Unsaturated Carboxylic Acids.

Project description:The direct enantioselective copper hydride (CuH)-catalyzed synthesis of β-chiral amides from α,β-unsaturated carboxylic acids and secondary amines under mild reaction conditions is reported. The method utilizes readily accessible carboxylic acids and tolerates a variety of functional groups in the β-position including several heteroarenes. A subsequent iridium-catalyzed reduction to γ-chiral amines can be performed in the same flask without purification of the intermediate amides.

| S-EPMC8027949 | biostudies-literature

Reduction of Carboxylic Acids to Alcohols via Manganese(I) Catalyzed Hydrosilylation.

Project description:The reduction of carboxylic acids to the respective alcohols, in mild conditions, was achieved using [MnBr(CO)5] as the catalyst and bench stable PhSiH3 as the reducing agent. It was shown that the reaction with the earth-abundant metal catalyst could be performed either with a catalyst loading as low as 0.5 mol %, rare with the use of [MnBr(CO)5], or on a gram scale employing only 1.5 equiv of PhSiH3, the lowest amount of silane reported to date for this transformation. Kinetic data and control experiments have provided initial insight into the mechanism of the catalytic process, suggesting that it proceeds via the formation of silyl ester intermediates and ligand dissociation to generate a coordinatively unsaturated Mn(I) complex as the active species.

| S-EPMC8395667 | biostudies-literature

Palladium-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylic Acids with Aryl Tosylates.

Project description:Decarboxylative coupling reactions of alkynyl carboxylic acids with aryl tosylates were developed in the presence of a palladium catalyst. Among the commercially available phosphine ligands, only 1-dicyclohexylphosphino-2-(di-tert-butylphosphino-ethyl)ferrocene (CyPF-tBu) showed good reactivity. The reaction took place smoothly and gave the decarboxylative coupled products in moderate to good yields. This demonstrates the excellent functional group tolerance toward alkyl, alkoxy, fluoro, thiophenyl, ester, and ketone groups. In addition, alkyl-substituted propiolic acids, such as octynoic and hexynoic acids, were coupled with phenyl tosylate to provide the desired products. We found that the electronic properties of the substituents on the phenyl ring in arylpropiolic acids are an important factor. The order of reactivity was found to be aryl iodide > aryl bromide > aryl tosylate > aryl chloride. However, aryl chloride-bearing electron-withdrawing groups showed higher reactivity than those bearing aryl tosylates.

| S-EPMC6644868 | biostudies-literature

Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates.

Project description:The direct asymmetric copper hydride (CuH)-catalyzed coupling of α,β-unsaturated carboxylic acids to aryl alkenes to access chiral α-aryl dialkyl ketones is reported. A variety of substrate substitution patterns, sensitive functional groups, and heterocycles are tolerated in this reaction, which significantly expands the range of accessible products compared with existing hydroacylation methodology. Although mechanistic studies are ongoing, we propose that CuH-catalyzed silylation of unsaturated acids occurs to access a uniquely effective acyl electrophilic coupling partner.

| S-EPMC5587210 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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