Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Investigation of the H-bond-mediated aglycone delivery reaction in application to the synthesis of ?-glucosides.

ABSTRACT: In an attempt to refine the H-bond-mediated Aglycone Delivery (HAD) glycosylation reaction reported herein is the synthesis of ?-glucosides using an ethylthio glucoside donor equipped with the remote 6-O-picoloyl substituent. Upon examining various aliphatic, aromatic, and carbohydrate acceptors, it was determined that both electronic and steric factors may greatly affect the stereoselectivity of the HAD reaction with this donor.

SUBMITTER: Mannino MP

PROVIDER: S-EPMC6215728 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Investigation of the H-bond-mediated aglycone delivery reaction in application to the synthesis of β-glucosides.

Mannino Michael P MP Yasomanee Jagodige P JP Demchenko Alexei V AV

Carbohydrate research 20180922

In an attempt to refine the H-bond-mediated Aglycone Delivery (HAD) glycosylation reaction reported herein is the synthesis of β-glucosides using an ethylthio glucoside donor equipped with the remote 6-O-picoloyl substituent. Upon examining various aliphatic, aromatic, and carbohydrate acceptors, it was determined that both electronic and steric factors may greatly affect the stereoselectivity of the HAD reaction with this donor. ...[more]

PMID: 30286335

Similar Datasets

Synthesis of pluraflavin A "aglycone".

Project description:The "aglycone" of pluraflavin A (2) has been synthesized. The key features of this synthesis include a 1,3-dipolar cycloaddition between a nitrile oxide (cf. 14) and an olefin (22) to yield an isoxazoline followed by subsequent conversion into the gamma-pyrone of pluraflavin A. The epoxide moiety linked to the pyrone is installed prior to Diels-Alder installation of the D ring, which allows access to a number of potentially active cytotoxic intermediates en route to the final compound. The preliminary in vitro results of two such compounds are also included with the racemic title compound exhibiting cytotoxicity in the nanomolar range.

| S-EPMC2638005 | biostudies-literature

Formal synthesis of (+)-brefeldin A: application of a zinc-mediated ring expansion reaction.

Project description:An efficient formal synthesis of (+)-brefeldin A was accomplished through a synthetic approach that relied upon three keys steps. The five-membered ring was generated in a stereocontrolled fashion through application of a tandem conjugate addition-intramolecular cyclization method developed by Toru. Ring-closing metathesis provided access to a twelve-membered beta-keto lactone, which was ring-expanded to the alpha,beta-unsaturated-gamma-keto lactone through a zinc carbenoid-mediated reaction. Conversion of this lactone to (+)-brefeldin A has been reported previously.

| S-EPMC2572133 | biostudies-literature

Approaches to polycyclic 1,4-dioxygenated xanthones. Application to total synthesis of the aglycone of IB-00208.

Project description:Hexacyclic xanthone natural products such as IB-00208 present a formidable challenge in organic synthesis. A new approach to polycyclic 1,4-dioxygenated xanthones from benzocyclobutenones has been developed and applied to the first total synthesis of the aglycone of IB-00208. The 22-step synthesis features an acetylide stitching process that joins an aryl aldehyde with an angularly fused benzocyclobutenone, which was prepared by a ring-closing metathesis reaction. The resulting acetylenic benzocyclobutenone diol underwent a Moore rearrangement to give an intermediate that was further elaborated to the aglycone of IB-00208 as a mixture of hydroquinone-quinone tautomers.

| S-EPMC4285456 | biostudies-literature

Enzymatic synthesis of novel phloretin glucosides.

Project description:A UDP-glycosyltransferase from Bacillus licheniformis was exploited for the glycosylation of phloretin. The in vitro glycosylation reaction confirmed the production of five phloretin glucosides, including three novel glucosides. Consequently, we demonstrated the application of the same glycosyltransferase for the efficient whole-cell biocatalysis of phloretin in engineered Escherichia coli.

| S-EPMC3648048 | biostudies-literature

Topological investigation of the reaction mechanism of glycerol carbonate decomposition by bond evolution theory.

Project description:The reaction mechanisms of the decomposition of glycerol carbonate have been investigated at the density functional theory level within the bond evolution theory. The four reaction pathways yield to 3-hydroxypropanal (TS1), glycidol (TS2a and TS2b), and 4-methylene-1,3-dioxolan-2-one (TS3). The study reveals non-concerted processes with the same number (four) of structural stability domains for each reaction pathway. For the two decarboxylation mechanisms, the two first steps are similar. They correspond to the cleavage of two single CO bonds to the detriment of the increased population of the lone pairs of two O atoms. These are followed, along TS1, by the transformation of a CO single bond into a double bond together with a proton transfer to create a CH bond. For TS2a and TS2b, the last step is a cyclization by CO bond formation. For the TS3 pathway, the first stage consists in the cleavage of a CH bond and the transfer of its electron population to both a proton and a C atom, the second step corresponds to the formation of an OH bond, and the last one describes the formation of a CC double bond. Moreover, the analysis of the energies, enthalpies, and free enthalpies of reaction and of activation leads to the conclusion that 3-hydroxypropanal is both the thermodynamic and kinetic product, independent of the method of calculation.

| S-EPMC8695523 | biostudies-literature

Development of a C-C Bond Cleavage/Vinylation/Mizoroki-Heck Cascade Reaction: Application to the Total Synthesis of 14- and 15-Hydroxypatchoulol.

Project description:A C-C bond cleavage/vinylation/Mizoroki-Heck cascade reaction has been developed to provide access to densely functionalized bicyclo[2.2.2]octane frameworks. The sequence proceeds through the coupling of dihydroxylated pinene derivatives, prepared from carvone, with gem-dichloroalkenes. The method was applied to 12-step total syntheses of both 14- and 15-hydroxypatchoulol, which provided unambiguous support for the structure of the natural products and corrects a misassignment in the isolation report.

| S-EPMC9635941 | biostudies-literature

Enantioselective synthesis of (+)-estrone exploiting a hydrogen bond-promoted Diels-Alder reaction.

Project description:Starting from Dane's diene and methylcyclopentenedione, (+)-estrone is synthesized along the Quinkert-Dane route in 24% total yield. The key step is an enantioselective Diels-Alder reaction promoted by an amidinium catalyst as efficiently as by a traditional Ti-TADDOLate Lewis acid.

| S-EPMC2852147 | biostudies-literature

Investigation of the regioselectivity for the staudinger reaction and its application for the synthesis of aminoglycosides with N-1 modification.

Project description:The criteria for controlling the regioselectivity of Staudinger reduction of azides have been investigated. These findings enable a convenient direct N-1 modification of the perazidoneamine and perazidoribostamycin resulting in the synthesis of aminoglycoside antibiotics with activity against drug-resistant bacteria.

| S-EPMC2553255 | biostudies-literature

Mechanistic Investigation of the Rhodium-Catalyzed Transfer Hydroarylation Reaction Involving Reversible C-C Bond Activation.

Project description:Carbon-carbon (C-C) bonds are ubiquitous but are among the least reactive bonds in organic chemistry. Recently, catalytic approaches to activate C-C bonds by transition metals have demonstrated the synthetic potential of directly reorganizing the skeleton of small molecules. However, these approaches are usually restricted to strained molecules or rely on directing groups, limiting their broader impact. We report a detailed mechanistic study of a rare example of catalytic C-C bond cleavage of unstrained alcohols that enables reversible ketone transfer hydroarylation under Rh-catalysis. Combined insight from kinetic analysis, in situ nuclear magnetic resonance (NMR) monitoring, and density functional theory (DFT) calculations supports a symmetric catalytic cycle, including a key reversible β-carbon elimination event. In addition, we provide evidence regarding the turnover-limiting step, the catalyst resting state, and the role of the sterically encumbered NHC ligand. The study further led to an improved catalytic system with the discovery of two air-stable precatalysts that showed higher activity for the transformation in comparison to the original conditions.

| S-EPMC10722515 | biostudies-literature

Sugar Silanes: Versatile Reagents for Stereocontrolled Glycosylation via Intramolecular Aglycone Delivery.

Project description:A new method for the intramolecular glycosylation of alcohols is described. Utilizing carbohydrate-derived silanes, the catalytic dehydrogenative silylation of alcohols is followed by intramolecular glycosylation. Appropriate combinations of silane position and protecting groups allow highly selective access to β-manno, α-gluco, or β-gluco stereochemical relationships as well as 2-azido-2-deoxy-β-gluco- and 2-deoxy-β-glucosides. Intramolecular aglycone delivery from the C-2 or C-6 position provides 1,2-cis or 1,2-trans glycosides, respectively. Multifunctional acceptor substrates such as hydroxyketones and diols are tolerated and are glycosylated in a site-selective manner.

| S-EPMC4435934 | 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