Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Establishing the absolute configuration of the asbestinins: enantioselective total synthesis of 11-acetoxy-4-deoxyasbestinin D.

ABSTRACT: A highly stereoselective synthesis of 11-acetoxy-4-deoxyasbestinin D (1) has been completed in 26 linear steps. The synthesis hinges on a selective glycolate aldol addition to establish the C-2 stereocenter, a ring-closing metathesis reaction to complete the oxonene, and an intramolecular Diels-Alder cycloaddition to establish the relative configuration at C-1, C-10, and C-14. This initial total synthesis of an asbestinin also serves to confirm the absolute configuration of this subclass of the C-2-C-11-cyclized cembranoid natural products.

SUBMITTER: Crimmins MT

PROVIDER: S-EPMC2546569 | biostudies-literature | 2005 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Establishing the absolute configuration of the asbestinins: enantioselective total synthesis of 11-acetoxy-4-deoxyasbestinin D.

Crimmins Michael T MT Ellis J Michael JM

Journal of the American Chemical Society 20051201 49

A highly stereoselective synthesis of 11-acetoxy-4-deoxyasbestinin D (1) has been completed in 26 linear steps. The synthesis hinges on a selective glycolate aldol addition to establish the C-2 stereocenter, a ring-closing metathesis reaction to complete the oxonene, and an intramolecular Diels-Alder cycloaddition to establish the relative configuration at C-1, C-10, and C-14. This initial total synthesis of an asbestinin also serves to confirm the absolute configuration of this subclass of the ...[more]

PMID: 16332064

Similar Datasets

Catalytic enantioselective alkylative dearomatization-annulation: total synthesis and absolute configuration assignment of hyperibone K.

Project description:The asymmetric total synthesis of the polyprenylated acylphloroglucinol hyperibone K has been achieved using an enantioselective alkylative dearomatization-annulation process. NMR and computational studies were employed to probe the mode of action of a chiral phase-transfer (ion pair) catalyst.

| S-EPMC2962984 | biostudies-literature

Total synthesis, structure revision, and absolute configuration of (-)-brevenal.

Project description:Total synthesis of structure 1 originally proposed for brevenal, a nontoxic polycyclic ether natural product isolated from the Florida red tide dinoflagellate, Karenia brevis, was accomplished. The key features of the synthesis involved (i) convergent assembly of the pentacyclic polyether skeleton based on our developed Suzuki-Miyaura coupling chemistry and (ii) stereoselective construction of the multi-substituted (E,E)-dienal side chain by using copper(I) thiophen-2-carboxylate (CuTC)-promoted modified Stille coupling. The disparity of NMR spectra between the synthetic material and the natural product required a revision of the proposed structure. Detailed spectroscopic comparison of synthetic 1 with natural brevenal, coupled with the postulated biosynthetic pathway for marine polyether natural products, suggested that the natural product was most likely represented by 2, the C26 epimer of the proposed structure 1. The revised structure was finally validated by completing the first total synthesis of (-)-2, which also unambiguously established the absolute configuration of the natural product.

| S-EPMC2575246 | biostudies-literature

Total synthesis, stereochemical reassignment, and absolute configuration of chlorofusin.

Project description: Not available

| S-EPMC2531192 | biostudies-literature

Assignment of absolute configuration to SCH 351448 via total synthesis.

Project description:The synthesis and absolute configuration of SCH 351448, an interesting ionophoric natural product, are reported herein. Mukaiyama aldol-Prins and segment-coupling Prins reactions were employed to construct the constituent tetrahydropyrans of SCH 351448. Efforts to assemble the C2-symmetric core of the natural product by a templated olefin metathesis strategy are described; however, a stepwise fragment assembly was ultimately utilized to complete the target molecule.

| S-EPMC2574719 | biostudies-literature

Asymmetric Alkylation of Anthrones, Enantioselective Total Synthesis of (-)- and (+)-Viridicatumtoxins B and Analogues Thereof: Absolute Configuration and Potent Antibacterial Agents.

Project description:A phase transfer catalyzed asymmetric alkylation of anthrones with cyclic allylic bromides using quinidine- or quinine-derived catalysts is described. Utilizing mild basic conditions and as low as 0.5 mol % catalyst loading, and achieving up to >99:1 dr selectivity, this asymmetric reaction was successfully applied to produce enantioselectively (-)- and (+)-viridicatumtoxins B, and thus allowed assignment of the absolute configuration of this naturally occurring antibiotic. While the developed asymmetric synthesis of C10 substituted anthrones is anticipated to find wider applications in organic synthesis, its immediate application to the construction of a variety of designed enantiopure analogues of viridicatumtoxin B led to the discovery of highly potent, yet simpler analogues of the molecule. These studies are expected to facilitate drug discovery and development efforts toward new antibacterial agents.

| S-EPMC5826551 | biostudies-literature

Total synthesis and absolute configuration of the bisanthraquinone antibiotic BE-43472B.

Project description:An-T-biotic: The first total synthesis of the T-shaped bisanthraquinone natural product BE-43472B was accomplished and its absolute configuration assigned. Key transformations in the pivotal cascade sequence include a Diels-Alder reaction, a hemiketal formation, and a nucleophilic aromatic ipso substitution.

| S-EPMC2678724 | biostudies-literature

Enantioselective photocycloaddition of 3-hydroxyflavones: total syntheses and absolute configuration assignments of (+)-ponapensin and (+)-elliptifoline.

Project description:We have previously reported development of biomimetic, asymmetric [3 + 2] photocycloadditions between 3-hydroxyflavones and cinnamate dipolarophiles to access (-)-rocaglamide and related natural products. Herein, we describe enantioselective syntheses of aglain cycloadducts leading to the first total syntheses and absolute configuration assignments of the aglain natural products (+)-ponapensin and (+)-elliptifoline.

| S-EPMC3529213 | biostudies-literature

Enantioselective total syntheses of nankakurines A and B: confirmation of structure and establishment of absolute configuration.

Project description:Total syntheses of (+)-nankakurine A (2) and (+)-nankakurine B (3) were accomplished by a sequence that employs an intramolecular dipolar cycloaddition of an azomethine imine intermediate to form the azatricyclic moiety and establish the relative configuration of the spiropiperidine ring. These syntheses, together with the synthesis of the originally purported structure 1 of nankakurine A, rigorously establish the relative and absolute configuration of these structurally unusual Lycopodium alkaloids. The syntheses are sufficiently concise that gram quantities of (+)-nankakurine A (2) and (+)-nankakurine B (3) will be available for further biological studies.

| S-EPMC3074941 | biostudies-literature

Total synthesis and determination of the absolute configuration of a natural analgesic: crotonine

Project description:We report the first total synthesis of four possible absolute configurations and four other regional isomers of a naturally occurring alkaloid crotonine, which was isolated from Croton tiglium L. (Euphoriaceae) without elucidation of its absolute configuration. The concise five-step route with a chirally poor and regioselective strategy starting from monosaccharides was established, and the absolute structure of the natural crotonine was determined by comparison of the NMR spectra and optical rotations of the synthetic products. Electronic Supplementary Material Supplementary material is available for this article at 10.1007/s13659-013-0080-1 and is accessible for authorized users.

| S-EPMC4131603 | biostudies-literature

Total synthesis and absolute configuration of laurenditerpenol: a hypoxia inducible factor-1 activation inhibitor.

Project description:The absolute stereo structure of the natural product laurenditerpenol (1S, 6R, 7S, 10R, 11R, 14S, 15R) has been accomplished from eight plausible stereoisomers by its first asymmetric total synthesis in a highly convergent and flexible synthetic pathway. Six stereoisomers of laurenditerpenol were synthesized and evaluated for their biological activity.

| S-EPMC2911032 | 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