Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Total synthesis of the reported structure of ceanothine D via a novel macrocyclization strategy.

ABSTRACT: The first total synthesis of the reported structure of ceanothine D, a cyclopeptide alkaloid found in red root, was achieved using a highly convergent synthetic strategy. Highlights of the synthesis include the first concomitant macrocyclization and formation of the unique chiral tertiary alkyl-aryl ether bond with complete regio- and stereo-control in the presence of a sensitive Z-enamide moiety to access the strained para-cyclophane present in its structure. This synthetic strategy may be broadly applicable in the generation of other structurally similar cyclopeptide alkaloids, enabling further biological and chemical investigations.

SUBMITTER: Lee J

PROVIDER: S-EPMC5909672 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Total synthesis of the reported structure of ceanothine D via a novel macrocyclization strategy.

Lee Jisun J Joullié Madeleine M MM

Chemical science 20180131 9

The first total synthesis of the reported structure of ceanothine D, a cyclopeptide alkaloid found in red root, was achieved using a highly convergent synthetic strategy. Highlights of the synthesis include the first concomitant macrocyclization and formation of the unique chiral tertiary alkyl-aryl ether bond with complete regio- and stereo-control in the presence of a sensitive Z-enamide moiety to access the strained para-cyclophane present in its structure. This synthetic strate ...[more]

PMID: 29732118

Similar Datasets

Total synthesis of the reported structure of 13a-hydroxytylophorine.

Project description:The first total synthesis of the reported structure of 13a-hydroxytylophorine was accomplished. The key step was an unprecedented NaBH4-promoted one-pot reductive cyclization cascade that efficiently yielded a hydroxyl azonane intermediate. The indolizidine framework was obtained by means of oxidation and a subsequent unexpected protecting-group migration. This total synthesis revealed that the reported structure of the naturally isolated compound is incorrect.

| S-EPMC5716997 | biostudies-literature

Total Synthesis of Gelsenicine via a Catalyzed Cycloisomerization Strategy.

Project description:The first total synthesis of (±)-gelsenicine is reported. The synthetic route is highly efficient (13 steps), featuring (1) a pivotal metal-catalyzed isomerization/rearrangement process that forges the central core of the molecule and (2) two facile C-N bond-forming steps that establish the flanking heterocycles.

| S-EPMC4732274 | biostudies-literature

Total synthesis of (+)-pilosinine via a stereodivergent conjugate addition strategy.

Project description:In recent work, asymmetric conjugate addition reactions to chiral 4-phenyl-N-enoyl-1,3-oxazolidinones have been shown to give different stereochemical outcomes depending on the conditions employed. Through the application of stereodivergent reaction conditions, the total synthesis of (+)-pilosinine and the formal synthesis of (-)-pilosinine has been completed from a single enantiomer of the 1,3-oxazolidi-none auxiliary.

| S-EPMC7288726 | biostudies-literature

Concise total synthesis of (+/-)-pseudotabersonine via double ring-closing metathesis strategy.

Project description:A concise synthesis of (+/-)-pseudotabersonine from commercially available 1-(phenylsulfonyl)-3-indolecarboxaldehyde has been accomplished. This synthesis features the convergent assembly of a key intermediate via a stepwise variant of a Mannich-type multicomponent coupling process, a double ring-closing metathesis, and a one-pot deprotection/cyclization reaction.

| S-EPMC2921645 | biostudies-literature

Macrocyclization by nickel-catalyzed, ester-promoted, epoxide-alkyne reductive coupling: total synthesis of (-)-gloeosporone.

Project description:Ringing the changes: The total synthesis of the title compound centers around a novel strategy that employs a nickel(0)-phosphine complex and triethyl borane in an efficient closure of a 14-membered ring through C--C bond formation (see scheme; cod=cyclooctadiene). The synthesis was accomplished in 10 steps and in approximately 9 % overall yield.

| S-EPMC2806845 | biostudies-literature

Total synthesis of complestatin: development of a Pd(0)-mediated indole annulation for macrocyclization.

Project description:Full details of the initial development and continued examination of a powerful intramolecular palladium(0)-mediated indole annulation for macrocyclization closure of the strained 16-membered biaryl ring system found in complestatin (1, chloropeptin II) and the definition of factors impacting its intrinsic atropodiastereoselectivity are described. Its examination and use in an alternative, second-generation total synthesis of complestatin are detailed in which the order of the macrocyclization reactions was reversed from our first-generation total synthesis. In this approach and with the ABCD biaryl ether ring system in place, the key Larock cyclization was conducted with substrate 36 (containing four phenols, five secondary amides, one carbamate, and four labile aryl chlorides) and provided the product 37 (56%) exclusively as a single atropisomer (>20:1, detection limits) possessing the natural (R)-configuration. In this instance, the complexity of the substrate and the reverse macrocyclization order did not diminish the atropodiastereoselectivity; rather, it provided an improvement over the 4:1 selectivity that was observed with the analogous substrate used to provide the isolated DEF ring system in our first-generation approach. Just as significant, the atroposelectivity represents a complete reversal of the diasteroselectivity observed with analogous macrocyclizations conducted using a Suzuki biaryl coupling.

| S-EPMC2892899 | biostudies-literature

Total synthesis of (-)-N-methylwelwitindolinone B isothiocyanate via a chlorinative oxabicycle ring-opening strategy.

Project description:The first total synthesis of N-methylwelwitindolinone B isothiocyanate is reported. The route features several key steps, including a regio- and diastereoselective chlorinative oxabicycle ring-opening reaction to introduce the challenging alkyl chloride motif.

| S-EPMC4206695 | biostudies-literature

The total synthesis of K-252c (staurosporinone) via a sequential C-H functionalisation strategy.

Project description:A synthesis of the bioactive indolocarbazole alkaloid K-252c (staurosporinone) via a sequential C-H functionalisation strategy is reported. The route exploits direct functionalisation reactions around a simple arene core and comprises of two highly-selective copper-catalysed C-H arylations, a copper-catalysed C-H amination and a palladium-catalysed C-H carbonylation, which build up the structural complexity of the natural product framework.

| S-EPMC5477024 | biostudies-literature

Vinyl sulfonamide synthesis for irreversible tethering via a novel ?-selenoether protection strategy.

Project description:Vinyl sulfonamides are valuable electrophiles for targeted protein modification and inhibition. We describe a novel approach to the synthesis of terminal vinyl sulfonamides which uses mild oxidative conditions to induce elimination of an ?-selenoether masking group. The method complements traditional synthetic approaches and typically yields vinyl sulfonamides in high purity after aqueous work-up without requiring column chromatography of the final electrophilic product. The methodology is applied to the synthesis of covalent fragments for use in irreversible protein tethering and crucially enables the attachment of diverse fragments to the vinyl sulfonamide warhead via a chemical linker. Using thymidylate synthase as a model system, ethylene glycol is identified as an effective linker for irreversible protein tethering.

| S-EPMC6349062 | biostudies-literature

A unified strategy for enantioselective total synthesis of cladiellin and briarellin diterpenes: total synthesis of briarellins E and F and the putative structure of alcyonin and revision of its structure assignment.

Project description:Enantioselective total syntheses of briarellin E (12) and briarellin F (13), as well as the structure originally proposed for the cladiellin diterpene alcyonin (10), have been realized. Comparison of the spectral data for synthetic 10, natural alcyonin, cladiellisin (33), and cladiellaperoxide (34), as well as chemical transformations of 10 and natural alcyonin, suggest that the structure of this coral metabolite is allylic peroxide 11. The unified approach detailed herein can be used to access both C4-deoxygenated and C4-oxygenated cladiellins and briarellins. The central step in these syntheses is acid-promoted condensation of (Z)-alpha,beta-unsaturated aldehydes 17 with cyclohexadienyl diols 18 to form intermediates 16 incorporating the hexahydroisobenzofuran core and five stereocenters of these marine diterpenes (Scheme 1 ).

| S-EPMC2744073 | biostudies-literature