Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Syntheses of carbocyclic uracil polyoxin C analogs: application of Pd(0)/InI-allylation of 4-acetoxy-2-azetidinone.

ABSTRACT: Carbocyclic uracil polyoxin C analogs are prepared from an acylnitroso-derived hetero Diels-Alder cycloadduct in fewer than nine steps. Pd(0)/InI-mediated allylation of 4-acetoxy-2-azetidinone is used to install the beta-amino acid side chain at the C-5' position of the carbocycle.

SUBMITTER: Cesario C

PROVIDER: S-EPMC2745051 | biostudies-literature | 2009 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Syntheses of carbocyclic uracil polyoxin C analogs: application of Pd(0)/InI-allylation of 4-acetoxy-2-azetidinone.

Cesario Cara C Miller Marvin J MJ

The Journal of organic chemistry 20090801 15

Carbocyclic uracil polyoxin C analogs are prepared from an acylnitroso-derived hetero Diels-Alder cycloadduct in fewer than nine steps. Pd(0)/InI-mediated allylation of 4-acetoxy-2-azetidinone is used to install the beta-amino acid side chain at the C-5' position of the carbocycle. ...[more]

PMID: 19514728

Similar Datasets

Pd(0)/InI-mediated allylic additions to 4-acetoxy-2-azetidinone: new route to highly functionalized carbocyclic scaffolds.

Project description:Acylnitroso-derived hetero-Diels-Alder cycloadducts are susceptible to C-O bond cleavage with Pd(0) and InI to form allylic indium(III) species. The in situ prepared allylindium compounds readily react at room temperature with Eschenmoser's salt. Allylation of 4-acetoxy-2-azetidinone provides derivatized cyclopentenes in high regio- and diastereoselectivity.

| S-EPMC2692034 | biostudies-literature

Syntheses of carbocyclic aminonucleosides and (-)-epi-4'-carbocyclic puromycin: Application of palladium(0)/indium iodide-allylations and tethered aminohydroxylations.

Project description:Carbocyclic aminonucleosides and epi-4'-carbocyclic puromycin were prepared from an acylnitroso-derived hetero Diels-Alder cycloadduct. Pd(0)/InI-mediated allylations of a formyl species were used to install the 4'-hydroxymethyl group. A tethered aminohydroxylation strategy was employed to install the cis-2',3'-aminoalcohol moiety with complete regio- and diastereocontrol.

| S-EPMC2903068 | biostudies-literature

Enantioselective syntheses of carbocyclic nuleosides 5'-homocarbovir, epi-4'-homocarbovir and their cyclopropylamine analogs using facially selective Pd-mediated allylations.

Project description:Carbocyclic nucleosides (-)-5'-homocarbovir and (+)-epi-4'-homocarbovir were prepared from an acylnitroso-derived hetero Diels-Alder cycloadduct. A kinetic enzymatic resolution generated an enantiopure aminocyclopentenol and Pd(0)-mediated decarboxylative allylations of allyl 2,2,2-trifluoroethyl malonates were used to install the 4'-hydroxyethyl groups. Late stage derivatization gave access to the cyclopropylamine congenors, (-)-5'-homoabacavir and (+)-epi-4'-homoabacavir. All carbonucleoside target molecules were evaluated for antiviral activity.

| S-EPMC3050557 | biostudies-literature

Synthesis of carbocyclic nucleoside analogs with five-membered heterocyclic nucleobases.

Project description:New carbocyclic nucleoside analogs with five-membered heterocyclic nucleobases were synthesized and evaluated as potential anti-HIV and anti-HCV agents. Among the synthesized carbocyclic nucleoside analogs, the pyrazole amide 15f exhibited modest selective anti-HIV-1 activity (EC50 = 24 µM).

| S-EPMC4446795 | biostudies-literature

DNA bending induced by carbocyclic sugar analogs constrained to the north conformation.

Project description:DNA bending caused by introduction of carbocyclic sugars constrained to the north conformation was studied, using explicit solvent molecular dynamic (MD) simulations. The native Drew-Dickerson (DD) dodecamer and its three modifications containing north carbocyclic sugars in the 7th (T7*), 8th (T8*) or both 7th and 8th (T7T8*) nucleotide positions were examined. Introduction of the carbocyclic sugar results in A-form conformations for the alpha, beta, chi, zeta, and sugar pucker backbone parameters in the modified nucleotides. Increased steric repulsion between the sugar and its parent base in the modified oligonucleotides impacts the roll and cup dinucleotide step parameters, increasing the bending of the oligomer axis. Increased buckling of the substituted nucleotides disrupts the usual stabilizing base stacking interactions. The level of overall bending depends on the number and position of carbocyclic sugars introduced in the DNA sequence. Single sugar substitutions are unable to induce substantial bending due to the neighboring unmodified nucleotides counterbalancing the distortion. Significant bending can, however, be induced by two consecutive north sugars (T7T8*), which is in agreement with experimental results. The modified oligomers populate a wide range of bend angles, indicating that they maintain flexibility in the bent state. The present results suggest that insertion of carbocyclic sugars into DNA or RNA duplexes can be used to engineer bending of the duplexes without impacting the electrostatic or chemical properties of the phosphodiester backbone, thereby serving as excellent tools for experimental elucidation of nucleic acid structure-function relationships.

| S-EPMC2873029 | biostudies-literature

Substrate-dependent dihydroxylation of substituted cyclopentenes: toward the syntheses of carbocyclic sinefungin and noraristeromycin.

Project description:Carbocyclic nucleosides are of considerable interest for the development of new therapeutic agents. A key reaction in the preparation of many such nucleoside analogues is dihydroxylation of appropriately substituted cyclopentenes. Although often considered a routine reaction, in this paper, we report the dramatic influence of substituents on the facial selectivity of dihydroxylations. The substituted cyclopentene substrates are derived from acylnitroso cycloaddition reactions of cyclopentadiene, followed by N-O reduction and efficient enzymatic resolution. The results are directly utilized in a very efficient asymmetric synthesis of an antiviral carbocyclic nucleoside, noraristeromycin 5. Extensions toward the synthesis of carbocyclic sinefungin 7 document the importance of realizing the substituent dependence of the dihydroxylation reaction.

| S-EPMC2652561 | biostudies-literature

Total Syntheses of 11-Acetoxy-4-deoxyasbestinin?D, 4-Deoxyasbestinin?C, Asbestinin-10, -20, -21 and -23.

Project description:Six members of the asbestinin family of marine diterpene natural products have been synthesized in an efficient and stereoselective manner from a single oxa-bridged intermediate. Five of these natural products have not been synthesized previously and the structures of four of them have been confirmed as those proposed originally or following revisions to the original structures. The fifth natural product-asbestinin-21-has been shown to be a diastereomer of the compound that had been proposed previously.

| S-EPMC7027880 | biostudies-literature

Syntheses and biological evaluation of ring-C modified colchicine analogs.

Project description:Ring-C modified alkaloids were synthesized from colchicine using iminonitroso Diels-Alder reactions in a highly regio- and stereoselective fashion. Several analogs exhibited cytotoxic activity similar to that of colchicine itself against PC-3 and MCF-7 cancer cell lines, by serving as prodrugs of colchicine through retro Diels-Alder reactions under the assayed conditions. In vitro microtubule polymerization assays indicated that these modifications affected their interaction with tubulin.

| S-EPMC2883562 | biostudies-literature

Pentafluorosulfanyl-containing flufenamic acid analogs: Syntheses, properties and biological activities.

Project description:Pentafluorosulfanyl-containing analogs of flufenamic acid have been synthesized in high yields. Computationally, pKa, LogP and LogD values have been determined. Initial bioactivity studies reveal effects as ion channel modulators and inhibitory activities on aldo-keto reductase 1C3 (AKR1C3) as well as COX-1 and COX-2.

| S-EPMC4599580 | biostudies-literature

Syntheses of new spirocarbocyclic nucleoside analogs using iminonitroso Diels-Alder reactions.

Project description:N-Cbz- and Boc-protected spirocyclic dienes were prepared by dialkylation of cyclopentadiene. These dienes coupled efficiently in a series of iminonitroso Diels-Alder reactions to produce a series of new spirocyclic adducts. Hydrogenolysis of these adducts afforded new spirocycles that contain multiple handles for further functionalization. Furthermore, stereocontrolled dihydroxylation and reductive cleavage of the spirocyclic adducts generated versatile scaffolds for the syntheses and derivatization of novel spirocyclic carbocyclic nucleoside analogs.

| S-EPMC2671554 | 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