Browse
Submit Data
Databases
API
Help

Dataset Information

9 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Site-selective acylation of natural products with BINOL-derived phosphoric acids.

ABSTRACT: The site-selective acylation of a steroidal natural product 19-hydroxydehydroepiandrosterone catalyzed by 1,1'-Bi(2-napthol)-derived (BINOL) chiral phosphoric acids (CPA's) is described. Systematic variation and multivariate linear regression analysis reveal that the same steric parameters typically needed for high enantioselectivity with this class of CPAs are also required for site-selectivity in this case. Density functional theory calculations identify additional weak CH-? interactions as contributors to site discrimination. We further report a rare example of site-selective acylation of phenols through the evaluation of naringenin, a flavonoid natural product, using CPA catalysis. These results suggest that BINOL-derived CPA's may have broader applications in site-selective catalysis.

SUBMITTER: Li J

PROVIDER: S-EPMC6905390 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Site-selective acylation of natural products with BINOL-derived phosphoric acids.

Li Junqi J Grosslight Samantha S Miller Scott J SJ Sigman Matthew S MS Toste F Dean FD

ACS catalysis 20191001 11

The site-selective acylation of a steroidal natural product 19-hydroxydehydroepiandrosterone catalyzed by 1,1'-Bi(2-napthol)-derived (BINOL) chiral phosphoric acids (CPA's) is described. Systematic variation and multivariate linear regression analysis reveal that the same steric parameters typically needed for high enantioselectivity with this class of CPAs are also required for site-selectivity in this case. Density functional theory calculations identify additional weak CH-π interactions as co ...[more]

PMID: 31827975

Similar Datasets

Selecting Chiral BINOL-Derived Phosphoric Acid Catalysts: General Model To Identify Steric Features Essential for Enantioselectivity.

Project description:Choosing the optimal catalyst for a new transformation is challenging because the ideal molecular requirements of the catalyst for one reaction do not always simply translate to another. Large groups at the 3,3' positions of the binaphthol rings are important for efficient stereoinduction but if they are too large this can lead to unusual or poor results. By applying a quantitative steric assessment of the substituents at the 3,3' positions of the binaphthol ring, we have systematically studied the effect of modulating this group on enantioselectivity for a wide range of reactions involving imines, and verified this analysis using ONIOM calculations. We have shown that in most reactions, the stereochemical outcome depends on both proximal and remote sterics. Summarising detailed calculations into a simple qualitative model identifies and explains the steric features required for high selectivity. This model is consistent with seventy seven papers reporting reactions (over 1000 transformations in total), and provides a straightforward decision tree for selecting the best catalyst.

| S-EPMC5656902 | biostudies-other

Gold and BINOL-phosphoric acid catalyzed enantioselective hydroamination/N-sulfonyliminium cyclization cascade.

Project description:A highly enantioselective hydroamination/N-sulfonyliminium cyclization cascade is reported using a combination of gold(I) and chiral phosphoric acid catalysts. An initial 5-exo-dig hydroamination and a subsequent phosphoric acid catalyzed cyclization process provide access to complex sulfonamide scaffolds in excellent yield and high enantiocontrol. The method can be extended to lactam derivatives, with excellent yields and enantiomeric excesses of up to 93% ee.

| S-EPMC3931332 | biostudies-literature

Total synthesis of (±)-decursivine via BINOL-phosphoric acid catalyzed tandem oxidative cyclization.

Project description:The synthesis of tetracyclic indole alkaloid (±)-decursivine was accomplished using BINOL-phosphoric acid catalyzed tandem oxidative cyclization as a key step with (bis(trifluoroacetoxy)iodo)benzene (PIFA) as an oxidizing agent. This represents one of the shortest and highest yielding routes for the synthesis of (±)-decursivine from readily available starting materials.

| S-EPMC8497573 | biostudies-literature

The Natural Products Atlas 2.0: a database of microbially-derived natural products.

Project description:Within the natural products field there is an increasing emphasis on the study of compounds from microbial sources. This has been fuelled by interest in the central role that microorganisms play in mediating both interspecies interactions and host-microbe relationships. To support the study of natural products chemistry produced by microorganisms we released the Natural Products Atlas, a database of known microbial natural products structures, in 2019. This paper reports the release of a new version of the database which includes a full RESTful application programming interface (API), a new website framework, and an expanded database that includes 8128 new compounds, bringing the total to 32 552. In addition to these structural and content changes we have added full taxonomic descriptions for all microbial taxa and have added chemical ontology terms from both NP Classifier and ClassyFire. We have also performed manual curation to review all entries with incomplete configurational assignments and have integrated data from external resources, including CyanoMetDB. Finally, we have improved the user experience by updating the Overview dashboard and creating a dashboard for taxonomic origin. The database can be accessed via the new interactive website at https://www.npatlas.org.

| S-EPMC8728154 | biostudies-literature

Chloromethyl-triazole: a new motif for site-selective pseudo-acylation of proteins.

Project description:Rapid, site-selective modification of cysteine residues with chloromethyl-triazole derivatives generates pseudo-acyl sLys motifs, mimicking important post-translational modifications. Near-native biotinylation of peptide and protein substrates is shown to be site-selective and modified histone H4 retains functional activity.

| S-EPMC5656099 | biostudies-literature

Site-selective aqueous C-H acylation of tyrosine-containing oligopeptides with aldehydes.

Project description:The development of useful synthetic tools to label amino acids within a peptide framework for the ultimate modification of proteins in a late-stage fashion is a challenging task of utmost importance within chemical biology. Herein, we report the first Pd-catalyzed C-H acylation of a collection of Tyr-containing peptides with aldehydes. This water-compatible tagging technique is distinguished by its site-specificity, scalability and full tolerance of sensitive functional groups. Remarkably, it provides straightforward access to a high number of oligopeptides with altered side-chain topology including mimetics of endomorphin-2 and neuromedin N, thus illustrating its promising perspectives toward the diversification of structurally complex peptides and chemical ligation.

| S-EPMC8162766 | biostudies-literature

Unified synthesis of caged Garcinia natural products based on a site-selective Claisen/Diels-Alder/Claisen rearrangement.

Project description:A unified synthetic strategy toward caged Garcinia natural products has been designed and implemented. Central to the strategy is a tandem Claisen/Diels-Alder/Claisen rearrangement of a suitably substituted xanthone precursor to form forbesione (1a). Serving as a template, forbesione is then used to deliver representative members of this family, including desoxygaudichaudione A (4), desoxymorellin (5), and gambogin (10). Studies on the timing of this reaction cascade suggest that the C-ring Claisen/Diels-Alder rearrangement proceeds initially and is followed by the A-ring Claisen reaction. The electronic and steric effects that govern the outcome of this cascade are presented.

| S-EPMC514429 | biostudies-literature

S-Adamantyl Group Directed Site-Selective Acylation: Applications in Streamlined Assembly of Oligosaccharides.

Project description:The site-selective functionalization of carbohydrates is an active area of research. Reported here is the surprising observation that the sterically encumbered adamantyl group directed site-selective acylation at the C2 position of S-glycosides through dispersion interactions between the adamantyl C-H bonds and the π system of the cationic acylated catalyst, which may have broad implications in many other chemical reactions. Because of their stability, chemical orthogonality, and ease of activation for glycosylation, the site-selective acylation of S-glycosides streamlines oligosaccharide synthesis and will have wide applications in complex carbohydrate synthesis.

| S-EPMC6663581 | biostudies-literature

Ligand-directed dibromophenyl benzoate chemistry for rapid and selective acylation of intracellular natural proteins.

Project description:A rapid and selective ligand-directed chemical reaction was developed for the acylation of proteins in living cells on the basis of ligand-directed chemistry. By fine tuning the reactivity and stability of the phenyl ester derivatives, we successfully identified ortho-dibromophenyl benzoate as the optimal reactive motif. It was sufficiently stable in an aqueous buffer, hydrolyzing less than 10% after 13 h of incubation, but reactive enough for efficient and selective protein labeling in living mammalian cells, as well as in vitro (referred to as ligand-directed dibromophenyl benzoate (LDBB) chemistry). Using this chemistry, various fluorophores can be tethered to the target protein directly, which allows fluorescence visualization of the labeled protein in live cells using different colored fluorophore groups (including coumarin, fluorescein and rhodamine). Furthermore, this labeling is applicable to not only an overexpressed protein (E. coli dihydrofolate reductase) but also endogenous human carbonic anhydrase II and XII under living cell conditions. LDBB chemistry is a new entry of ligand-directed protein labeling methods, and should be particularly useful for the imaging of natural proteins in living cells.

| S-EPMC5490417 | biostudies-literature

Antimicrobial Nanomaterials Derived from Natural Products-A Review.

Project description:Modern medicine has relied heavily on the availability of effective antibiotics to manage infections and enable invasive surgery. With the emergence of antibiotic-resistant bacteria, novel approaches are necessary to prevent the formation of biofilms on sensitive surfaces such as medical implants. Advances in nanotechnology have resulted in novel materials and the ability to create novel surface topographies. This review article provides an overview of advances in the fabrication of antimicrobial nanomaterials that are derived from biological polymers or that rely on the incorporation of natural compounds with antimicrobial activity in nanofibers made from synthetic materials. The availability of these novel materials will contribute to ensuring that the current level of medical care can be maintained as more bacteria are expected to develop resistance against existing antibiotics.

| S-EPMC5502919 | biostudies-other

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