Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Fluorinated Amine Stereotriads via Allene Amination.

ABSTRACT: The incorporation of fluorine into organic scaffolds often improves the bioactivity of pharmaceutically relevant compounds. C-F/C-N/C-O stereotriad motifs are prevalent in antivirals, neuraminidase inhibitors, and modulators of androgen receptors, but are challenging to install. An oxidative allene amination strategy using Selectfluor rapidly delivers triply functionalized triads of the form C-F/C-N/C-O, exhibiting good scope and diastereoselectivity for all syn products. The resulting stereotriads are readily transformed into fluorinated pyrrolidines and protected ?-, ?-, and ?-amino acids.

SUBMITTER: Liu L

PROVIDER: S-EPMC5541934 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Fluorinated Amine Stereotriads via Allene Amination.

Liu Lu L Gerstner Nels C NC Oxtoby Lucas J LJ Guzei Ilia A IA Schomaker Jennifer M JM

Organic letters 20170602 12

The incorporation of fluorine into organic scaffolds often improves the bioactivity of pharmaceutically relevant compounds. C-F/C-N/C-O stereotriad motifs are prevalent in antivirals, neuraminidase inhibitors, and modulators of androgen receptors, but are challenging to install. An oxidative allene amination strategy using Selectfluor rapidly delivers triply functionalized triads of the form C-F/C-N/C-O, exhibiting good scope and diastereoselectivity for all syn products. The resulting stereotri ...[more]

PMID: 28573862

Similar Datasets

Oxidative allene amination for the synthesis of azetidin-3-ones.

Project description:Regioselectivity in the aziridination of silyl-substituted homoallenic sulfamates is readily diverted to the distal double bond of the allene to yield endocyclic bicyclic methyleneaziridines with excellent stereocontrol. Subsequent reaction with electrophilic oxygen sources initiates facile rearrangement to densely functionalized, fused azetidin-3-ones in excellent d.r., effectively transferring the axial chirality of the allene to central chirality in the products. The steric nature of the silyl group dictates which of the two rings of the fused azetidin-3-one will undergo further functionalization, providing an additional element of diversity for the preparation of enantioenriched azetidine scaffolds with potential biological activity.

| S-EPMC4701577 | biostudies-literature

Synthesis of Functionalized Azepines via Cu(I)-Catalyzed Tandem Amination/Cyclization Reaction of Fluorinated Allenynes.

Project description:An efficient method for the selective preparation of trifluoromethyl-substituted azepin-2-carboxylates and their phosphorous analogues has been developed via Cu(I)-catalyzed tandem amination/cyclization reaction of functionalized allenynes with primary and secondary amines.

| S-EPMC9416787 | biostudies-literature

A general carbonyl alkylative amination for tertiary amine synthesis.

Project description:The ubiquity of tertiary alkylamines in pharmaceutical and agrochemical agents, natural products and small-molecule biological probes1,2 has stimulated efforts towards their streamlined synthesis3-9. Arguably the most robust method for the synthesis of tertiary alkylamines is carbonyl reductive amination3, which comprises two elementary steps: the condensation of a secondary alkylamine with an aliphatic aldehyde to form an all-alkyl-iminium ion, which is subsequently reduced by a hydride reagent. Direct strategies have been sought for a 'higher order' variant of this reaction via the coupling of an alkyl fragment with an alkyl-iminium ion that is generated in situ10-14. However, despite extensive efforts, the successful realization of a 'carbonyl alkylative amination' has not yet been achieved. Here we present a practical and general synthesis of tertiary alkylamines through the addition of alkyl radicals to all-alkyl-iminium ions. The process is facilitated by visible light and a silane reducing agent, which trigger a distinct radical initiation step to establish a chain process. This operationally straightforward, metal-free and modular transformation forms tertiary amines, without structural constraint, via the coupling of aldehydes and secondary amines with alkyl halides. The structural and functional diversity of these readily available precursors provides a versatile and flexible strategy for the streamlined synthesis of complex tertiary amines.

| S-EPMC7116815 | biostudies-literature

Enantioselective direct α-amination of aldehydes via a photoredox mechanism: a strategy for asymmetric amine fragment coupling.

Project description:The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated N-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Importantly, this photoinduced transformation allows direct and enantioselective access to α-amino aldehyde products that do not require postreaction manipulation.

| S-EPMC3786402 | biostudies-literature

Regioselective allene hydroarylation via one-pot allene hydrosilylation/Pd-catalyzed cross-coupling.

Project description:Advances in hydroarylation have been achieved by the development of a one-pot regioselective allene hydrosilylation/Pd(0)-catalyzed cross-coupling protocol. The regioselectivity is primarily governed by N-heterocyclic carbene (NHC) ligand identity in the hydrosilylation step and is preserved in the subsequent cross-coupling reaction. This methodology affords streamlined access to functionalized 1,1-disubstituted alkenes with excellent regiocontrol.

| S-EPMC4201326 | biostudies-literature

Allene functionalization via bicyclic methylene aziridines.

Project description:The oxidative functionalization of olefins is a common method for the formation of vicinal carbon-heteroatom bonds. However, oxidative methods to transform allenes into synthetic motifs containing three contiguous carbon-heteroatom bonds are much less developed. This paper describes the use of bicyclic methylene aziridines (MAs), prepared via intramolecular allene aziridination, as scaffolds for functionalization of all three allene carbons.

| S-EPMC3090038 | biostudies-literature

Synthesis of 1,3-diaminated stereotriads via rearrangement of 1,4-diazaspiro[2.2]pentanes.

Project description:The synthesis of 1,3-diaminated stereotriads via the bis-aziridination of allenes is reported. The reactive 1,4-diazaspiro[2.2]pentane intermediates undergo a mild Brønsted acid-promoted rearrangement to yield 1,3-diaminated ketones in good yields with excellent stereocontrol. Directed reduction of the ketone can be achieved to yield a C-N/C-O/C-N stereotriad in high dr. The ability to transfer the axial chirality of the substrates to the products allows for the facile preparation of enantioenriched stereotriads from allenes in two simple steps.

| S-EPMC4490830 | biostudies-literature

Amine dehydrogenases: efficient biocatalysts for the reductive amination of carbonyl compounds.

Project description:Amines constitute the major targets for the production of a plethora of chemical compounds that have applications in the pharmaceutical, agrochemical and bulk chemical industries. However, the asymmetric synthesis of α-chiral amines with elevated catalytic efficiency and atom economy is still a very challenging synthetic problem. Here, we investigated the biocatalytic reductive amination of carbonyl compounds employing a rising class of enzymes for amine synthesis: amine dehydrogenases (AmDHs). The three AmDHs from this study - operating in tandem with a formate dehydrogenase from Candida boidinii (Cb-FDH) for the recycling of the nicotinamide coenzyme - performed the efficient amination of a range of diverse aromatic and aliphatic ketones and aldehydes with up to quantitative conversion and elevated turnover numbers (TONs). Moreover, the reductive amination of prochiral ketones proceeded with perfect stereoselectivity, always affording the (R)-configured amines with more than 99% enantiomeric excess. The most suitable amine dehydrogenase, the optimised catalyst loading and the required reaction time were determined for each substrate. The biocatalytic reductive amination with this dual-enzyme system (AmDH-Cb-FDH) possesses elevated atom efficiency as it utilizes the ammonium formate buffer as the source of both nitrogen and reducing equivalents. Inorganic carbonate is the sole by-product.

| S-EPMC5486444 | biostudies-literature

Chemoselective allene aziridination via Ag(I) catalysis.

Project description:Allene aziridination generates useful bicyclic methylene aziridine scaffolds that can be flexibly transformed into a range of stereochemically complex and densely functionalized amine-containing stereotriads. The scope of this chemistry has been limited by the poor chemoselectivity that often results when typical dinuclear Rh(II) catalysts are employed with homoallenic carbamates. Herein, Ag(I) catalysts that significantly improve the scope and yield of bicyclic methylene aziridines that can be prepared via allene aziridination are described.

| S-EPMC4490828 | biostudies-literature

Fluorinated rhodacyanines induce apoptosis via mitochondrial damage and cell cycle arrest

Project description:Rhodacyanine, a series of cyanines derived from rhodanine, exerts anticancer effects. This study intended to uncover the biological mechanism underlying the anticancer effects of a a fluorinated rhodacyanine in HeLa cervical cancer cells. Initially, the cytotoxic activities of 15 compounds were screened, Rho-7 exhibited the most effective compound against Hela cell growth with IC50 values at 0.03 µM. Interestingly, Rho-7-targeted mitochondrial damage leads to cancer cell death by increasing reactive oxygen species (ROS) levels. Additionally, Rho-7 can trigger Hela cells to undergo apoptosis and cell cycle arrest at the G2/M phase. Rho-7 could downregulate the expression of anti-apoptotic Mcl-1 genes or upregulate the level of pro-apoptotic Bad and Bik genes. Our findings suggest that the anticancer activity of Rho-7 involve ROS generation, cell cycle arrest and apoptotic induction, as well as alteration of pro-and anti-apoptotic genes, displaying a therapeutic potential of Rho-7 in cervical cancer treatment.

2024-01-01 | GSE251969 | GEO

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