Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

An "aprotic" Tamao oxidation/syn-selective tautomerization reaction for the efficient synthesis of the C1-C9 fragment of fludelone.

ABSTRACT: An efficient synthesis of the C(1)-C(9) fragment of fludelone has been developed. The key step is a tandem silylformylation-crotylsilylation/Tamao oxidation sequence that establishes the C(5) ketone, the C(6), C(7), and C(8) stereocenters, and the C(9) alkene in a single operation from a readily accessed starting material. The stereochemical outcome at C(6) depends critically on the development of an "aprotic" Tamao oxidation, which leads to a reversal in the intrinsic diastereoselectivity observed using "standard" Tamao oxidation conditions.

SUBMITTER: Harrison TJ

PROVIDER: S-EPMC3466590 | biostudies-literature | 2012 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

An "aprotic" Tamao oxidation/syn-selective tautomerization reaction for the efficient synthesis of the C1-C9 fragment of fludelone.

Harrison Tyler J TJ Rabbat Philippe M A PM Leighton James L JL

Organic letters 20120905 18

An efficient synthesis of the C(1)-C(9) fragment of fludelone has been developed. The key step is a tandem silylformylation-crotylsilylation/Tamao oxidation sequence that establishes the C(5) ketone, the C(6), C(7), and C(8) stereocenters, and the C(9) alkene in a single operation from a readily accessed starting material. The stereochemical outcome at C(6) depends critically on the development of an "aprotic" Tamao oxidation, which leads to a reversal in the intrinsic diastereoselectivity obser ...[more]

PMID: 22950417

Similar Datasets

A formal synthesis of the C1-C9 fragment of amphidinolide C employing the Tamaru reaction.

Project description:Homoallylation of aldehydes with isoprene and triethylborane catalyzed by Ni(acac)(2) gave hydroxyalkenes in good yield with excellent regio- and stereoselectivity. Cross metathesis of the hydroxyalkenes with methyl acrylate using second-generation Grubbs catalyst and copper(I) iodide afforded alpha,beta-unsaturated esters, which underwent cyclization in the presence of DBU to produce tetrahydrofurans with the correct relative configuration for the C1-C9 fragment of amphidinolides C, C2, and F.

| S-EPMC2896498 | biostudies-literature

Asymmetric alcohol C-H allylation and syn-crotylation: C9-C20 of tetrafibricin.

Project description:The C9-C20 segment of the fibrinogen receptor inhibitor tetrafibricin was prepared in 10 steps (longest linear sequence). Ruthenium catalyzed enantioselective syn-crotylation is used to construct C9-C13. Iridium catalyzed asymmetric alcohol C-H allylation of a commercial malic acid derived alcohol is used to construct C14-C20. Recovery and recycling of the iridium catalyst is described.

| S-EPMC3932543 | biostudies-literature

Synthesis of β-hydroxy-α-haloesters through super silyl ester directed syn-selective aldol reaction.

Project description:Super silyl haloesters including chloro- and bromoacetate were synthesized and utilized for aldol reactions to give syn-β-hydroxy-α-haloacetates in good yields with high diastereoselectivities. β-Hydroxy-α-fluoroacetate was obtained by lithiation of super silyl bromofluoroacetate. Sequential Darzens reactions provided cis-glycidic esters in moderate yields.

| S-EPMC3946542 | biostudies-literature

Synthesis of the C1-C52 fragment of amphidinol 3, featuring a beta-alkoxy alkyllithium addition reaction.

Project description:An advanced intermediate for the synthesis of amphidinol 3 has been prepared. A cross-metathesis reaction was used to couple the C1-C12 and C13-C26 segments. An unusual beta-alkoxy alkyllithium reagent was generated from this segment and added to a Weinreb amide to assemble the C1-C52 section of amphidinol 3. These compounds represent some of the most advanced intermediates reported to date for the synthesis of amphidinol 3.

| S-EPMC2496920 | biostudies-literature

Studies on a urea-directed Stork-Crabtree hydrogenation. Synthesis of the C1-C9 subunit of (+)-zincophorin.

Project description:A detailed account on the stereoselective synthesis of the C1-C9 subunit of (+)-zincophorin is described here. This approach features the first application of a stereoselective inverse electron demand hetero-[4 + 2] cycloaddition of chiral allenamides in natural product synthesis. The C1-C9 subunit matches Cossy's intermediate, thereby constituting a formal total synthesis. In addition, details of an unusual urea-directed Stork-Crabtree hydrogenation observed during these efforts are also disclosed here.

| S-EPMC2562543 | biostudies-literature

Tautomerization-dependent recognition and excision of oxidation damage in base-excision DNA repair.

Project description:NEIL1 (Nei-like 1) is a DNA repair glycosylase guarding the mammalian genome against oxidized DNA bases. As the first enzymes in the base-excision repair pathway, glycosylases must recognize the cognate substrates and catalyze their excision. Here we present crystal structures of human NEIL1 bound to a range of duplex DNA. Together with computational and biochemical analyses, our results suggest that NEIL1 promotes tautomerization of thymine glycol (Tg)-a preferred substrate-for optimal binding in its active site. Moreover, this tautomerization event also facilitates NEIL1-catalyzed Tg excision. To our knowledge, the present example represents the first documented case of enzyme-promoted tautomerization for efficient substrate recognition and catalysis in an enzyme-catalyzed reaction.

| S-EPMC4948311 | biostudies-literature

Enantioselective synthesis of the C1-C11 fragment of tedanolide C.

Project description:A convergent synthesis of the protected C(1)-C(11) fragment 6 of the targeted enantiomer of tedanolide C is described. The key step of the synthesis is the Felkin-Ahn addition of vinyl iodide 7 to aldehyde 8 that proceeds in 80% yield with 4:1 diastereoselectivity.

| S-EPMC3539184 | biostudies-literature

Stereoselective synthesis of the C9-C19 fragment of lyngbyaloside B and C via ether transfer.

Project description:A stereoselective synthesis of the C9-C19 fragment of lyngbyaloside B and C highlighted, by an extension of our ether transfer methodology, enables the formation of tertiary ethers. 2-Naphthylmethyl ethers have been shown to proceed efficiently through ether transfer with high stereoselectivity and are easily deprotected by DDQ oxidation. Variation of the workup conditions results in the stereoselective formation of syn-1,3-diol mono- or diethers.

| S-EPMC3391344 | biostudies-literature

The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes.

Project description:By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electro-reduction reactions of HF, water and methanesulfonic acid (MSA) on the single crystal (111) facets of Au, Pt, Ir and Cu in organic aprotic electrolytes, 1 M LiPF6 in EC/EMC 3:7W (LP57), the aprotic electrolyte commonly used in Li-ion batteries, 1 M LiClO4 in EC/EMC 3:7W and 0.2 M TBAPF6 in 3 : 7 EC/EMC. In our previous work, we have established that LiF formation, accompanied by H2 evolution, is caused by a reduction of HF impurities and requires the presence of Li at the interface, which catalyzes the HF dissociation. In the present paper, we find that the measured potential of the electrochemical response for these reduction reactions correlates with the work function of the electrode surfaces and that the work function determines the potential for Li+ adsorption. The reaction path is investigated further by electrochemical simulations suggesting that the overpotential of the reaction is related to stabilizing the active structure of the interface having adsorbed Li+. Li+ is needed to facilitate the dissociation of HF which is the source of protons. Further experiments on other proton sources, water and methanesulfonic acid, show that if the hydrogen evolution involves negatively charged intermediates, F- or HO-, a cation at the interface can stabilize them and facilitate the reaction kinetics. When the proton source is already significantly dissociated (in the case of a strong acid), there is no negatively charged intermediate and thus the hydrogen evolution can proceed at much lower overpotentials. This reveals a situation where the overpotential for electrocatalysis is related to stabilizing the active structure of the interface, facilitating the reaction rather than providing the reaction energy.

| S-EPMC8152617 | biostudies-literature

Electrochemically Deposited Amorphous Cobalt-Nickel-Doped Copper Oxide as an Efficient Electrocatalyst toward Water Oxidation Reaction.

Project description:Production of hydrogen through water splitting is one of the green and the most practical solutions to cope with the energy crisis and greenhouse effect. However, oxygen evolution reaction (OER) being a sluggish step, the use of precious metal-based catalysts is the main impediment toward the viability of water splitting. In this work, amorphous copper oxide and doped binary- and ternary-metal oxides (containing CoII, NiII, and CuII) have been prepared on the surface of fluorine-doped tin oxide by a facile electrodeposition route followed by thermal treatment. The fabricated electrodes have been employed as efficient binder-free OER electrocatalysts possessing a high electrochemical surface area due to their amorphous nature. The cobalt-nickel-doped copper oxide (ternary-metal oxide)-based electrode showed promising OER activity with a high current density of 100 mA cm-2 at 1.65 V versus RHE that escalates to 313 mA cm-2 at 1.76 V in alkaline media at pH 14. The high activity of the ternary-metal oxide-based electrode was further supported by a smaller semicircle in the Nyquist plot. Furthermore, all metal-oxide-based electrodes offered high stability when tested for continuous production of oxygen for 50 h. This work highlights the synthesis of efficient and cost-effective amorphous metal-based oxide catalysts to execute electrocatalytic OER employing an electrodeposition approach.

| S-EPMC8340103 | 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