Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

The total synthesis of D-chalcose and its C-3 epimer.

ABSTRACT: We completed a new and efficient synthesis of D-chalcose (I) and the first synthesis of its C-3 epimer (I') in nine steps with overall yields of 23% and 24%, respectively. The key steps in the sequence were the formation of the stereocenter on C3 via Grignard reaction, the introduction of the stereogenic center on C2 by Sharpless asymmetric dihydroxylation, the protection of the C1 and C2 hydroxy groups with tert-butyldimethylsilyl trifluoromethanesulfonate (TBSOTf), and the selective cleavage of the primary OTBS ether using catalytic DL-10-camphorsulfonic acid (CSA) in MeOH.

SUBMITTER: Sun J

PROVIDER: S-EPMC3869251 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

The total synthesis of D-chalcose and its C-3 epimer.

Sun Jun J Fan Song S Wang Zhan Z Zhang Guoning G Bao Kai K Zhang Weige W

Beilstein journal of organic chemistry 20131122

We completed a new and efficient synthesis of D-chalcose (I) and the first synthesis of its C-3 epimer (I') in nine steps with overall yields of 23% and 24%, respectively. The key steps in the sequence were the formation of the stereocenter on C3 via Grignard reaction, the introduction of the stereogenic center on C2 by Sharpless asymmetric dihydroxylation, the protection of the C1 and C2 hydroxy groups with tert-butyldimethylsilyl trifluoromethanesulfonate (TBSOTf), and the selective cleavage o ...[more]

PMID: 24367425

Similar Datasets

Total Synthesis and Biological Evaluation of Ipomoeassin F and Its Unnatural 11R-Epimer.

Project description:Ipomoeassin F, a macrolide glycoresin containing an embedded disaccharide, possesses potent in vitro antitumor activity with an unknown mechanism of function. It inhibits tumor cell growth with single-digit nanomolar IC50 values, superior to many clinical chemotherapeutic drugs. To facilitate translation of its bioactivity into protein function for drug development, we report here a new synthesis for the gram-scale production of ipomoeassin F (3.8% over 17 linear steps) from commercially available starting materials. The conformation-controlled subtle reactivity differences of the hydroxyl groups in carbohydrates were utilized to quickly construct the disaccharide core, which, along with judicial selection of protecting groups, made the current synthesis very efficient. The same strategy was also applied to the smooth preparation of the 11R-epimer of ipomoeassin F for the first time. Cytotoxicity assays demonstrated the crucial role of the natural 11S configuration. In addition, cell cycle analyses and apoptosis assays on ipomoeassin F and/or its epimer were conducted. This work has laid a solid foundation for understanding the medicinal potential of the ipomoeassin family of glycolipids in the future.

| S-EPMC4651627 | biostudies-literature

Total synthesis of the spirocyclic imine marine toxin (-)-gymnodimine and an unnatural C4-epimer.

Project description:The first total synthesis of the marine toxin (-)-gymnodimine (1) has been accomplished in a convergent manner. A highly diastereo- and enantioselective exo-Diels-Alder reaction catalyzed by a bis-oxazoline Cu(II) catalyst enabled rapid assembly of the spirocyclic core of gymnodimine. The preparation of the tetrahydrofuran fragment utilized a chiral auxiliary based anti-aldol reaction. Two major fragments, spirolactam 56 and tetrahydrofuran 55, were then coupled through an efficient Nozaki-Hiyama-Kishi reaction. An unconventional, ambient temperature t-BuLi-initiated intramolecular Barbier reaction of alkyl iodide 64 was employed to form the macrocycle. A late stage vinylogous Mukaiyama aldol addition of a silyloxyfuran to a complex cyclohexanone 83 appended the butenolide, and a few additional steps provided (-)-gymnodimine (1). A diastereomer of the natural product was also synthesized, C4-epi-gymnodimine (90), derived from the vinylogous Mukaiyama aldol addition.

| S-EPMC3256008 | biostudies-literature

Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer.

Project description:In this article, we report the total synthesis of 6-deoxydihydrokalafungin (DDHK), a key biosynthetic intermediate of a dimeric benzoisochromanequinone antibiotic, actinorhodin (ACT), and its epimer, epi-DDHK. Tricyclic hemiacetal with 3-siloxyethyl group was subjected to Et3SiH reduction to establish the 1,3-cis stereochemistry in the benzoisochromane, and a subsequent oxidation/deprotection sequence then afforded epi-DDHK. A bicyclic acetal was subjected to AlH3 reduction to deliver the desired 1,3-trans isomer in an approximately 3:1 ratio, which was subjected to a similar sequence to that used for the 1,3-cis isomer that successfully afforded DDHK. A semisynthetic approach from (S)-DNPA, an isolable biosynthetic precursor of ACT, was also examined to afford DDHK and its epimer, which are identical to the synthetic products.

| S-EPMC8587838 | biostudies-literature

Total Synthesis and Biological Evaluation of Apratoxin E and Its C30 Epimer: Configurational Reassignment of the Natural Product.

Project description:Apratoxin E provided the inspiration for the design of apratoxin A/E hybrids under preclinical development. Through total synthesis using two different strategies, it was determined that the originally proposed configuration of the thiazoline at C30 is opposite from that in apratoxin A, in contrast to previous assumptions on biosynthetic grounds. The epimer and true natural apratoxin E were synthesized, and the biological activities were evaluated.

| S-EPMC5386831 | biostudies-literature

Stereocontrolled total synthesis of the potent anti-inflammatory and pro-resolving lipid mediator resolvin D3 and its aspirin-triggered 17R-epimer.

Project description:The first total synthesis of stereochemically pure resolvin D3 and aspirin-triggered resolvin D3 is reported. These enzymatic metabolites of docosahexaenoic acid (DHA) have potent anti-inflammatory and pro-resolving actions. The convergent synthetic strategy is based on enantiomerically pure starting materials, and it is highly stereocontrolled.

| S-EPMC3696528 | biostudies-literature

An efficient synthesis of the 4'-epimer of 2-fluoronoraristeromycin.

Project description:The 4'-epimer of 2-fluoronoraristeromycin was synthesized by employing bis-t-butoxycarbonyl (Boc) protected 2-fluoroadenine as a superior substrate for the Mitsunobu reaction with the appropriate cyclopentenol. Unlike the unsubstituted counterpart 2-fluoroadenine, this substrate is completely soluble in THF and resulted in a very good yield in the Mitsunobu coupling reaction as well as subsequent steps.

| S-EPMC3370682 | biostudies-literature

A convergent synthesis of carbocyclic sinefungin and its C5 epimer.

Project description:A convergent synthesis of carbocyclic sinefungin 2 and its C5 epimer 3 is described. The key features in our synthesis include the use of commercial available L-methionine and readily available (1R, 4S)-4-hydroxy-2-cyclopentenyl acetate as starting materials, cross-metathesis coupling, enzymatic kinetic resolution and Staudinger reduction. The current synthesis is flexible and therefore provides convenient access to the synthesis of various carbocyclic SIN analogues for biological evaluation.

| S-EPMC4267295 | biostudies-literature

First total synthesis of the pro-resolving lipid mediator 7(S),12(R),13(S)-Resolvin T2 and its 13(R)-epimer.

Project description:The first total synthesis of the pro-resolving lipid mediator 7(S),12(R),13(S)-Resolvin T2 [7(S), 12(R), 13(S)-RvT2] and its 13(R)-epimer, derived from n-3 docosapentaenoic acid (n-3 DPA), are described. 7(S), 12(R), 13(S)-RvT2 and its 13(R)-epimer were obtained by total synthesis using a chiral pool strategy to introduce the chiral centers. C7 was generated from S-(-)-1,2,4-butanetriol in both molecules and the C12 and C13 centers were generated from L-(+)-ribose and D-(-)-arabinose respectively. Cis and trans-selective Wittig reactions, selective deprotections, and Dess-Martin periodinane oxidation were the key steps in the syntheses.

| S-EPMC7454203 | biostudies-literature

Synthesis and biological evaluation of the [d-MeAla(11)]-epimer of coibamide A.

Project description:Coibamide A is a highly potent antiproliferative cyclic depsipeptide, which was originally isolated from a Panamanian marine cyanobacterium. In this study, the synthesis of coibamide A has been investigated using Fmoc-based solid-phase peptide synthesis followed by the cleavage of the resulting linear peptide from the resin and its subsequent macrolactonization. The peptide sequence of the linear coibamide A precursor was constructed on a solid-support following the optimization of the coupling conditions, where numerous coupling agents were evaluated. The macrocyclization of the resulting linear peptide provided the [d-MeAla(11)]-epimer of coibamide A, which exhibited nanomolar cytotoxic activity towards a number of human cancer cell lines.

| S-EPMC4342349 | biostudies-literature

En Route to Furan-Fused Naphthopyrones: Formal Synthesis of the (+)-Lasionectrin and Its C12-Epimer.

Project description:Despite the vast presence of the furan-fused naphthopyrone (FFN) skeleton in many bioactive natural products, such as lasionectrin, at present, a general approach to FFNs has not been developed yet. For that reason, a simple and straightforward synthetic approach consisting of a sequential procedure of a Diels-Alder reaction between 1,3-dimethoxy-benzocyclobutenol I and furan-fused-α,β-unsaturated-δ-lactones II (via an ο-quinodimethane intermediate III) followed by an oxidative aromatization of the corresponding Diels-Alder adduct IV is reported. Subsequently, the formal synthesis of the (+)-lasionectrin and its C12-epimer was achieved, the latter in only six steps.

| S-EPMC10729057 | 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