Browse
Submit Data
Databases
API
Help

Dataset Information

12 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Huckins JR

PROVIDER: S-EPMC2496920 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

A highly convergent synthesis of the C1-C31 polyol domain of amphidinol 3 featuring a TST-RCM reaction: confirmation of the revised relative stereochemistry.

Project description:The concise enantioselective synthesis of the revised C1-C31 fragment of the polyketide amphidinol 3 was accomplished in 16 steps and 12.8% overall yield. Salient features of the strategy include chemoselective Weinreb amide coupling and concomitant CBS reduction for the preparation of the C1-C15 tris-syn-1,5-diol motif and a temporary silicon-tethered ring-closing metathesis (TST-RCM) reaction in combination with a diastereoselective hydroboration for the construction of the C16-C31 polypropionate fragment. The union of the fragments was accomplished by a regioselective ring-opening of the terminal epoxide with a phenyl sulfone stabilized carbanion, which upon reduction and deprotection permits a comparison of the relative configuration with the natural product.

| S-EPMC5507186 | biostudies-literature

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

Synthesis of C<sub>70</sub>-fragment buckybowls bearing alkoxy substituents.

Project description:Buckybowls bearing a C70 fragment having two alkoxy groups were synthesized and their structural and optical properties were investigated by single crystal X-ray analysis and UV-vis spectroscopy. In the synthesis of dioxole derivative 5b, the regioisomer 5c was also produced. The yield of 5c was increased by increasing the reaction temperature, indicating that the rearrangement might involve the equilibrium between the Pd(IV) intermediates through C-H bond activation.

| S-EPMC7176931 | biostudies-literature

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

Project description: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.

| S-EPMC3466590 | biostudies-literature

Polyol synthesis with beta-oxyanionic alkyllithium reagents: syntheses of aculeatins A, B, and D.

Project description:Synthesis of ketone aldol products using a non-aldol route was developed. The beta-phenylthio alcohols were prepared from optically pure oxiranes. Deprotonation and reductive lithiation generated the key intermediate, a beta-oxyanionic alkyllithium reagent. Addition to a Weinreb amide produced the beta-hydroxy ketone in >90% yield using only 1.5 equiv of the phenylthio alcohol. Stereoselective reduction of the ketone led to either the syn- or anti-1,3-diol. This simple, convergent sequence was used to prepare aculeatins A, B, and D from a common intermediate.

| S-EPMC2741543 | 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

Enantioselective synthesis of beta-(3-hydroxypyrazol-1-yl) ketones using an organocatalyzed Michael addition reaction.

Project description:Beta-(3-hydroxypyrazol-1-yl) ketones have been prepared in high yields and excellent enantioselectivities (94-98% ee) via a Michael addition reaction between 2-pyrazolin-5-ones and aliphatic acyclic alpha,beta-unsaturated ketones using 9-epi-9-amino-9-deoxyquinine as the catalyst. These results account for the first example of an aza-Michael addition of the ambident 2-pyrazolin-5-one anion to a Michael acceptor.

| S-EPMC2752151 | biostudies-literature

Stereochemically versatile synthesis of the C1-C12 fragment of tedanolide C.

Project description:A flexible synthesis of the C1-C12 fragment of Tedanolide C has been accomplished in eight steps from 2-methyl-2,4-pentadienal. Asymmetric hydroformylation of a 1,3-diene allows for the late-stage generation of either C10 epimer with complete catalyst control. Diastereoselective addition of an isobutyryl ?-ketoester dianion to an ?,?-disubstituted chiral aldehyde sets the C5 stereochemistry while installing the geminal dimethyl unit. Differential protection of a syn-1,3-diol is performed as a highly efficient single-pot operation.

| S-EPMC3312041 | biostudies-literature

The Davis-Beirut reaction: N1,N2-disubstituted-1H-indazolones via 1,6-electrophilic addition to 3-alkoxy-2H-indazoles.

Project description:A variety of electrophiles (anhydrides, acid chlorides, carbonochloridates, sulfonyl chlorides, and alkyl bromides) react with 3-methoxy-2H-indazole (1a), benzoxazin[3,2-b]indazole (1d), and oxazolino[3,2-b]indazole (1e)?-?substrates available by the Davis-Beirut reaction?-?to yield a diverse set of N(1),N(2)-disubstituted-1H-indazolones. With certain electrophiles, an AERORC (Addition of the Electrophile, Ring Opening, and Ring Closure) process on indazole 1d results in indazoloindazolone formation. An intriguing aspect of these N(1),N(2)-disubstituted-1H-indazolones is that they are poised for diversification through, for example, azide-alkyne cycloaddition chemistry reported here.

| S-EPMC3112251 | biostudies-literature

A chemical synthesis of 11-methoxy mitragynine pseudoindoxyl featuring the interrupted Ugi reaction.

Project description:A synthesis of 11-methoxy mitragynine pseudoindoxyl, a new member of the mitragynine class of opioid agonists, from a derivative of the Geissman-Waiss lactone is described. An internal attack of an electron-rich aromatic ring on an electrophilic nitrilium ion and a late-stage construction of the functionalized piperidine ring by the method of reductive cyclization are the pivotal transformations; both ring annulations proceed in a highly diastereoselective fashion. The construction of substituted indoxyl frameworks by the interrupted Ugi method offers an attractive alternative to the strategy of oxidatively rearranging indoles.

| S-EPMC3714104 | 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