Browse
Submit Data
Databases
API
Help

Dataset Information

16 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Biomimetic approach to the catalytic enantioselective synthesis of tetracyclic isochroman.

ABSTRACT: Polyketide oligomers containing the structure of tetracyclic isochroman comprise a large class of natural products with diverse activity. However, a general and stereoselective method towards the rapid construction of this structure remains challenging due to the inherent instability and complex stereochemistry of polyketide. By mimicking the biosynthetic pathway of this structurally diverse set of natural products, we herein develop an asymmetric hetero-Diels-Alder reaction of in-situ generated isochromene and ortho-quinonemethide. A broad range of tetracyclic isochroman frameworks are prepared in good yields and excellent stereoinduction (up to 95% ee) from readily available α-propargyl benzyl alcohols and 2-(hydroxylmethyl) phenols under mild conditions. This direct enantioselective cascade reaction is achieved by a Au(I)/chiral Sc(III) bimetallic catalytic system. Experimental studies indicate that the key hetero-Diels-Alder reaction involves a stepwise pathway, and the steric hindrance between in-situ generated isochromene and t-Bu group of Sc(III)/N,N'-dioxide complex is responsible for the enantioselectivity in the hetero-Diels-Alder reaction step.

SUBMITTER: Lin X

PROVIDER: S-EPMC8368254 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Biomimetic Approach to the Catalytic Enantioselective Synthesis of Flavonoids.

Project description:Herein is reported the direct asymmetric addition of phenol nucleophiles to benzopyrylium salts as a means to produce enantioenriched flavonoid-like compounds. This enantioselective C-C bond construction was achieved through a chiral anion phase-transfer strategy that mimics the proposed biosynthesis of this structurally diverse set of natural products. The utility of this methodology was demonstrated in enantioselective synthesis of a 2,8-dioxabicyclo[3.3.1]nonane and a 2,4-diarylbenzopyran.

| S-EPMC5149420 | biostudies-literature

Biomimetic synthesis of the tetracyclic core of berkelic acid.

Project description:Acid-catalyzed condensation of 2,6-dihydroxybenzoic acid 3 with ketal aldehyde 14 in methanol at 25 degrees C, followed by CH2N2 esterification, gave a 4:1:4:1 mixture of diastereomers 15b-18b in 60% yield. Equilibration of this mixture with TFA in CDCl3 provided tetracycle 15b (83% yield) with the complete skeleton of berkelic acid. A similar condensation at 0 degrees C afforded 15b-18b and a reduction product 19b, which was probably formed by a 1,5-hydride shift.

| S-EPMC2527759 | biostudies-literature

General Enantioselective and Stereochemically Divergent Four-Stage Approach to Fused Tetracyclic Terpenoid Systems.

Project description:Tetracyclic terpenoid-derived natural products are a broad class of medically relevant agents that include well-known steroid hormones and related structures, as well as more synthetically challenging congeners such as limonoids, cardenolides, lanostanes, and cucurbitanes, among others. These structurally related compound classes present synthetically disparate challenges based, in part, on the position and stereochemistry of the numerous quaternary carbon centers that are common to their tetracyclic skeletons. While de novo syntheses of such targets have been a topic of great interest for over 50 years, semisynthesis is often how synthetic variants of these natural products are explored as biologically relevant materials and how such agents are further matured as therapeutics. Here, focus was directed at establishing an efficient, stereoselective, and molecularly flexible de novo synthetic approach that could offer what semisynthetic approaches do not. In short, a unified strategy to access common molecular features of these natural product families is described that proceeds in four stages: (1) conversion of epichlorohydrin to stereodefined enynes, (2) metallacycle-mediated annulative cross-coupling to generate highly substituted hydrindanes, (3) tetracycle formation by stereoselective forging of the C9-C10 bond, and (4) group-selective oxidative rearrangement that repositions a quaternary center from C9 to C10. These studies have defined the structural features required for highly stereoselective C9-C10 bond formation and document the generality of this four-stage synthetic strategy to access a range of unique stereodefined systems, many of which bear stereochemistry/substitution/functionality not readily accessible from semisynthesis.

| S-EPMC9438405 | biostudies-literature

Catalytic, Enantioselective Synthesis of Allenyl Boronates.

Project description:A method to achieve enantioselective 1,4-hydroboration of terminal enynes to access allenyl boronates under CuH catalysis is described. The reaction typically proceeds in a highly stereoselective manner and tolerates an array of synthetically useful functional groups. The utility of the enantioenriched allenyl boronate products is demonstrated through several representative downstream derivatizations.

| S-EPMC6364988 | biostudies-literature

Convergent and Biomimetic Enantioselective Total Synthesis of (-)-Communesin F.

Project description:The first biomimetic enantioselective total synthesis of (-)-communesin F based on a late-stage heterodimerization and aminal exchange is described. Our synthesis features the expedient diazene-directed assembly of two advanced fragments to secure the congested C3a-C3a' linkage in three steps, followed by a highly efficient biogenetically inspired aminal reorganization to access the heptacyclic communesin core in only two additional steps. Enantioselective syntheses of the two fragments were developed, with highlights including the catalytic asymmetric halocyclization and diastereoselective oxyamination reactions of tryptamine derivatives, a stereoselective sulfinimine allylation, and an efficient cyclotryptamine-C3a-sulfamate synthesis by either a new silver-promoted nucleophilic amination or a rhodium-catalyzed C-H amination protocol. The versatile syntheses of the fragments, their stereocontrolled assembly, and the efficient aminal exchange as supported by in situ monitoring experiments, in addition to the final stage N1'-acylation of the communesin core, provide a highly convergent synthesis of (-)-communesin F.

| S-EPMC4944760 | biostudies-literature

Catalytic enantioselective synthesis of 2-aryl-chromenes.

Project description:An enantioselective Pd-catalyzed 6-endo-trig reaction for the synthesis of 2-aryl-chromenes has been developed. A systematic optimization of a TADDOL-derived ligand set resulted in the identification of a novel monodentate phosphoramidite-palladium catalyst that accesses 2-aryl-2H-chromenes with high yield and enantioselectivity under mild conditions. The products obtained from this method can be transformed into biologically active compounds through functionalization of the chromene alkene.

| S-EPMC4334165 | biostudies-literature

Catalytic enantioselective total synthesis of (+)-eucomic acid.

Project description:A catalytic enantioselective synthesis of (+)-eucomic acid is reported. A palladium-catalyzed asymmetric allylic alkylation is employed to access the chiral tetrasubstituted α-hydroxyacid moiety found in the natural product. The protecting group strategy was investigated, and a protecting group manipulation was made without any appreciable deleterious effects in the allylic alkylation reaction. Non-natural (+)-eucomic acid is synthesized in a longest linear sequence of 13 steps.

| S-EPMC4986999 | biostudies-literature

Catalytic Enantioselective Synthesis of Difluorinated Alkyl Bromides.

Project description:We report an iodoarene-catalyzed enantioselective synthesis of β,β-difluoroalkyl bromide building blocks. The transformation involves an oxidative rearrangement of α-bromostyrenes, utilizing HF-pyridine as the fluoride source and m-CPBA as the stoichiometric oxidant. A catalyst decomposition pathway was identified, which, in tandem with catalyst structure-activity relationship studies, facilitated the development of an improved catalyst providing higher enantioselectivity with lower catalyst loadings. The versatility of the difluoroalkyl bromide products was demonstrated via highly enantiospecific substitution reactions with suitably reactive nucleophiles. The origins of enantioselectivity were investigated using computed interaction energies of simplified catalyst and substrate structures, providing evidence for both CH-π and π-π transition state interactions as critical features.

| S-EPMC7537710 | biostudies-literature

Highly enantioselective catalytic synthesis of chiral pyridines.

Project description:General methods to prepare chiral pyridine derivatives are greatly sought after due to their significance in medicinal chemistry. Here, we report highly enantioselective catalytic transformations of poorly reactive ?-substituted alkenyl pyridines to access a wide range of alkylated chiral pyridines. The simple methodology involves reactivity enhancement via Lewis acid (LA) activation, the use of readily available and highly reactive Grignard reagents, and a copper-chiral diphosphine ligand catalyst. Apart from allowing the introduction of different linear, branched, cyclic, and functionalised alkyl chains at the ?-position of alkenyl pyridines, the catalytic system also shows high functional group tolerance.

| S-EPMC5727103 | biostudies-other

A catalytic highly enantioselective allene approach to oxazolines.

Project description:Oxazolines are a very important class of heterocyclic compounds. However, catalytic enantioselective syntheses are very limited. Here, a highly enantioselective palladium-catalyzed coupling-cyclization of readily available N-(buta-2,3-dienyl) amides with aryl or 1-alkenyl iodides has been developed for the asymmetric construction of oxazoline derivatives. Many synthetically useful functional groups are tolerated in this reaction. The absolute configuration of the chiral center in the products has been established by X-ray diffraction study. A model for prediction of the absolute configuration of the chiral center in the products from this cyclic enantioselective nucleophilic allylation has been proposed. The synthetic potentials based on the unique structure of the products formed have also been demonstrated.

| S-EPMC5909368 | 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