Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Progress toward a Convergent, Asymmetric Synthesis of Jervine.

ABSTRACT: Progress toward a convergent approach for the enantioselective synthesis of the Veratrum alkaloid jervine is presented. The two requisite fragments were stereoselectively and efficiently fashioned from economical and readily available reagents. Key reactions include (a) a highly diastereoselective Ireland-Claisen rearrangement to establish the necessary cis-relationship between the amine and methyl group on the tetrahydrofuran E-ring; (b) a diastereoselective selenoetherification reaction that enabled the assembly of the D/E oxaspiro[4.5]decene in the needed configuration; and (c) an enzymatic desymmetrization of an abundant achiral diol en route to a key four-carbon building block as a practical alternative to a protected Roche ester reduction.

SUBMITTER: Zavesky BP

PROVIDER: S-EPMC7212305 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Progress toward the De Novo Asymmetric Synthesis of Euphanes.

Project description:Progress toward an asymmetric synthesis of euphanes is described. A C14-desmethyl euphane system possessing five differentially substituted and electronically distinct alkenes has been prepared. The route employed is based on sequential metallacycle-mediated annulative cross-coupling, double asymmetric Brønsted acid mediated intramolecular Friedel-Crafts alkylation, and an oxidative rearrangement to establish the requisite C10 quaternary center. These studies have also led to the discovery of a novel euphane-based modulator of the Liver X Receptor.

| S-EPMC9419992 | biostudies-literature

Convergent Catalytic Asymmetric Synthesis of Esters of Chiral Dialkyl Carbinols.

Project description:Because chiral dialkyl carbinols, as well as their derived esters, are significant as intermediates and end points in fields such as organic, pharmaceutical, and biological chemistry, the development of efficient approaches to their asymmetric synthesis is an important endeavor. In this report, we describe a method for the direct catalytic enantioselective synthesis of such esters, beginning with an alkyl halide (derived from an aldehyde and an acyl bromide), an olefin, and a hydrosilane, catalyzed by nickel, an earth-abundant metal. The method is versatile, tolerating substituents that vary in size and that bear a range of functional groups. We further describe a four-component variant of this process, wherein the alkyl halide is generated in situ, thus obviating the need to isolate either an alkyl electrophile or an alkylmetal, while still effecting an alkyl-alkyl coupling. Finally, we apply our convergent method to the efficient catalytic enantioselective synthesis of three esters that are bioactive themselves or that have been utilized in the synthesis of bioactive compounds.

| S-EPMC7580270 | biostudies-literature

Progress toward the total synthesis of frondosin C.

Project description:A straightforward approach toward the total synthesis of frondosin C is described. This strategy involves a key one-pot, microwave-assisted 5-exo cyclization-Claisen rearrangement sequence that was used for the expedient assembly of the frondosic C scaffold. Subsequent manipulation of the tetracyclic core allowed the synthesis of an advanced intermediate bearing the characteristic diene moiety in the B ring. [reaction: see text]

| S-EPMC2523271 | biostudies-literature

Progress toward the total synthesis of psymberin/irciniastatin A.

Project description:In this paper, we describe our synthesis of four key building blocks for the total synthesis of psymberin (1) and its C4 epimer (2). Despite early difficulties in processing material to the advanced intermediate stage, we have been successful in developing high-yielding syntheses for the pyran core, natural side chain, 4-epi side chain, and aryl fragments of the molecule. Our findings from the optimization process are presented herein.

| S-EPMC2736341 | biostudies-literature

Asymmetric synthesis of dihydroindanes by convergent alkoxide-directed metallacycle-mediated bond formation.

Project description:A convergent synthesis of highly substituted and stereodefined dihydroindanes is described from alkoxide-directed Ti-mediated cross-coupling of internal alkynes with substituted 4-hydroxy-1,6-enynes (substrates that derive from 2-directional functionalization of readily available epoxy alcohol derivatives). In addition to describing a new and highly stereoselective approach to bimolecular [2 + 2 + 2] annulation that delivers products not available with other methods in this area of chemical reactivity, evidence is provided to support annulation by way of regioselective alkyne-alkyne coupling, followed by metal-centered [4 + 2] rather than stepwise alkene insertion and reductive elimination. Overall, the reaction proceeds with exquisite stereochemical control and defines a convenient, convergent, and enantiospecific entry to fused carbocycles of great potential value in target-oriented synthesis and medicinal chemistry.

| S-EPMC3275653 | biostudies-literature

Progress toward the total synthesis of Bielschowskysin: a stereoselective [2+2] photocycloaddition.

Project description:The tetracyclic core of the diterpene bielschowskysin has been prepared as a single enantiomer via a stereoselective intramolecular [2+2] photocycloaddition of 5-alkylidene-2(5H)-furanone 3.

| S-EPMC2527052 | biostudies-literature

Studies toward the asymmetric synthesis of the right part of the mycalamides.

Project description:Described herein is the asymmetric synthesis of a functionalized, trioxadecalin unit that comprises the right-hand part of the mycalamides and related natural products. The synthetic route involves a 16-step sequence that accomplishes the formation of two heterocyclic rings and the generation of five stereocenters. The synthesis commenced with a C2-symmetric starting material, diethyl D-tartrate, and took advantage of a relay of diastereoselective reactions to extend this four-carbon chain and introduce new chiral centers. Subsequent electrophile-mediated cyclization afforded the desired pyran ring, which was then transformed into the desired, functionalized trioxadecalin skeleton.

| S-EPMC2517629 | biostudies-literature

Progress toward the Total Synthesis of Jogyamycin Using a Tandem Ichikawa/Winstein Rearrangement.

Project description:Jogyamycin is a densely functionalized aminocyclopentitol that displays potent antiprotozoal activity. Herein, we report a route toward this natural product that utilizes an unprecedented transformation involving a tandem Ichikawa-Winstein rearrangement to install the C-1/C-2 diamine core. Attempts to further functionalize the C-3/C-4 alkene en route to jogyamycin are also discussed.

| S-EPMC10789149 | biostudies-literature

A highly convergent approach toward (-)-brevenal.

Project description:Progress toward a highly convergent, asymmetric synthesis of brevenal is reported. Construction of the AB-ring and E-ring cyclic ether fragments was achieved through asymmetric alkylation/ring-closing metathesis strategies. A Horner-Wadsworth-Emmons olefination was used in a key bond-forming step to couple the advanced cyclic fragments and enable rapid access to the AB-E ring system.

| S-EPMC2878377 | biostudies-literature

Progress Toward a Large-Scale Synthesis of Molnupiravir (MK-4482, EIDD-2801) from Cytidine.

Project description:Molnupiravir (MK-4482, EIDD-2801) is a promising orally bioavailable drug candidate for the treatment of COVID-19. Herein, we describe a supply-centered and chromatography-free synthesis of molnupiravir from cytidine, consisting of two steps: a selective enzymatic acylation followed by transamination to yield the final drug product. Both steps have been successfully performed on a decagram scale: the first step at 200 g and the second step at 80 g. Overall, molnupiravir has been obtained in a 41% overall isolated yield compared to a maximum 17% isolated yield in the patented route. This route provides many advantages to the initial route described in the patent literature and would decrease the cost of this pharmaceutical should it prove safe and efficacious in ongoing clinical trials.

| S-EPMC8153789 | 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