Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Enantioselective palladium-catalyzed C(sp2)–C(sp2) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones† † Electronic supplementary information available. CCDC 2024499. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/d1sc04558j

ABSTRACT: Catalytic asymmetric variants for functional group transformations based on carbon–carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp2)–C(sp2) σ bond activation and click desymmetrization to form synthetically versatile and value-added oxaspiro products. The operationally straightforward and enantioselective palladium-catalyzed atom-economic annulation process exploits a TADDOL-derived bulky P-ligand bearing a large cavity to control enantioselective spiro-annulation that converts cyclopropenones and cyclic 1,3-diketones into chiral oxaspiro cyclopentenone–lactone scaffolds with good diastereo- and enantio-selectivity. The click-like reaction is a successful methodology with a facile construction of two vicinal carbon quaternary stereocenters and can be used to deliver additional stereocenters during late-state functionalization for the synthesis of highly functionalized or more complex molecules. An unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C–C bond activation and desymmetrization was developed for the enantioselective construction of synthetically versatile and value-added oxaspiro products with up to 95% ee.

SUBMITTER: Zhou H

PROVIDER: S-EPMC8549799 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Selenide-catalyzed enantioselective synthesis of trifluoromethylthiolated tetrahydronaphthalenes by merging desymmetrization and trifluoromethylthiolation.

Project description:Trifluoromethylthiolated molecules are an important class of biologically active compounds and potential drug candidates. Because of the lack of efficient synthetic methods, catalytic enantioselective construction of these molecules is rare and remains a challenge. To expand this field, we herein disclose a bifunctional selenide-catalyzed approach for the synthesis of various chiral trifluoromethylthiolated tetrahydronaphthalenes bearing an all-carbon quaternary stereocenter with gem-diaryl-tethered alkenes and alkynes by merging desymmetrization and trifluoromethylthiolation strategy. The products are obtained in high yields with excellent enantio- and diastereo-selectivities. This method can be applied to the desymmetrization and sulfenylation of diols as well. Computational studies reveal that selenide can activate the electrophilic reagent better than sulfide, confirming the higher efficiency of selenide catalysis in these reactions. On the basis of the theoretical calculations, an acid-derived anion-binding interaction is suggested to exist in the whole pathway and accounts for the observed high selectivities.

| S-EPMC5802806 | biostudies-literature

Palladium-Catalyzed, Enantioselective Desymmetrization of N-Acylaziridines with Indoles.

Project description:Ring opening reactions of meso-aziridines generate chiral amine derivatives where the control of stereochemistry is possible through enantioselective catalysis. We report the use of a diphosphine-palladium(II) catalyst for the highly enantioselective desymmetrization of N-acylaziridines with indoles. The β-tryptamine products are isolated in moderate to high yield across a range of indole and aziridine substitution patterns. The synthetic utility of β-tryptamine products is demonstrated by conversion to the brominated pyrroloindoline derivative.

| S-EPMC9022218 | biostudies-literature

Palladium-catalyzed regio- and enantioselective migratory allylic C(sp3)-H functionalization.

Project description:Transition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp3)-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp3)-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pKa values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process.

| S-EPMC8463607 | biostudies-literature

Enantioselective palladium/copper-catalyzed C-C σ-bond activation synergized with Sonogashira-type C(sp3)-C(sp) cross-coupling alkynylation.

Project description:The Sonogashira-type cross-coupling reaction is one of the most significant alkynylation transformations in organic chemistry. However, highly enantioselective alkynylation via the Sonogashira-type cross-coupling reaction is rather limited, mainly due to the difficulties in matching the stereoselective induction of chiral ligands with the combinational behavior of Pd/Cu-based bimetallic catalysts. We herein report novel enantioselective palladium/copper-catalyzed alkyl alkynylation of cyclobutanones with terminal alkynes via tandem C-C bond activation/Sonogashira-type cross coupling reaction, in which a novel chiral TADDOL-derived phosphoramidite ligand bearing fluorine and silicon-based bulky groups simplified as TFSi-Phos is found to be an efficient ligand for both C(sp2)-C(sp3) bond cleavage and new C(sp3)-C(sp) bond formation. A wide range of chiral alkynylated indanones bearing an all-carbon quaternary stereocenter are obtained efficiently with up to 97.5 : 2.5 er.

| S-EPMC6761865 | biostudies-other

Palladium-Catalyzed Enantioselective Csp3-Csp3 Cross-Coupling for the Synthesis of (Poly)fluorinated Chiral Building Blocks.

Project description:A general method for the enantioselective synthesis of carbo- and heterocyclic carbonyl compounds bearing fluorinated α-tetrasubstituted stereocenters using palladium-catalyzed decarboxylative allylic alkylation is described. The stereoselective Csp3-Csp3 cross-coupling reaction delivers five- and six-membered ketone and lactam products bearing (poly)fluorinated tetrasubstituted chiral centers in high yields and enantioselectivities. These fluorinated, stereochemically rich building blocks hold potential value in medicinal chemistry and are prepared using an orthogonal and enantioselective approach into such chiral moieties compared to traditional approaches, often without the use of electrophilic fluorinating reagents.

| S-EPMC6192028 | biostudies-literature

Merging C(sp3)-H activation with DNA-encoding.

Project description:DNA-encoded library (DEL) technology has the potential to dramatically expedite hit identification in drug discovery owing to its ability to perform protein affinity selection with millions or billions of molecules in a few experiments. To expand the molecular diversity of DEL, it is critical to develop different types of DNA-encoded transformations that produce billions of molecules with distinct molecular scaffolds. Sequential functionalization of multiple C-H bonds provides a unique avenue for creating diversity and complexity from simple starting materials. However, the use of water as solvent, the presence of DNA, and the extremely low concentration of DNA-encoded coupling partners (0.001 M) have hampered the development of DNA-encoded C(sp3)-H activation reactions. Herein, we report the realization of palladium-catalyzed C(sp3)-H arylation of aliphatic carboxylic acids, amides and ketones with DNA-encoded aryl iodides in water. Notably, the present method enables the use of alternative sets of monofunctional building blocks, providing a linchpin to facilitate further setup for DELs. Furthermore, the C-H arylation chemistry enabled the on-DNA synthesis of structurally-diverse scaffolds containing enriched C(sp3) character, chiral centers, cyclopropane, cyclobutane, and heterocycles.

| S-EPMC8162953 | biostudies-literature

Scaffolding catalysts: highly enantioselective desymmetrization reactions.

Project description:Ex-changing places: a highly enantioselective desymmetrization of 1,2-diols has been developed in which the catalyst utilizes reversible covalent bonding to the substrate to achieve both high selectivity and rate acceleration (see scheme, PMP=pentalmethylpiperidine, TBS=tert-butyldimethylsilyl). Induced intramolecularity is responsible for the enhanced rate, thus allowing the reaction to be performed at room temperature.

| S-EPMC3366164 | biostudies-literature

Enantioselective Copper-Catalyzed sp2/sp3 Diborylation of 1-Chloro-1-Trifluoromethylalkenes.

Project description:Fluorine-containing organoboron compounds have emerged as novel building blocks in chemical synthesis; among them, fluorinated sp2/sp3 diborylated compounds are particularly appealing, since they might undergo chemoselective and diversified transformations of different C-B bonds with fluorinated functionality, thus bringing versatility and complexity to the eventual products. However, expedient, synthetic strategies for the construction of such fluorinated diborylative compounds are very sparse. Herein, we disclose enantioselective Cu-catalyzed sp2/sp3 diborylations of 1-chloro-1-trifluoromethylalkenes, leading to diborylated compounds bearing a gem-difluoroalkenyl moiety; most intriguingly, the new formed C-B bonds include one stereoselective and optically pure Csp3-B bond. Further transformations on the eventual products demonstrated the values of our presented strategy.

| S-EPMC9413839 | biostudies-literature

Silacyclization through palladium-catalyzed intermolecular silicon-based C(sp2)-C(sp3) cross-coupling.

Project description:Silicon-based cross-coupling has been recognized as one of the most reliable alternatives for constructing carbon-carbon bonds. However, the employment of such reaction as an efficient ring expansion strategy for silacycle synthesis is comparatively little known. Herein, we develop the first intermolecular silacyclization strategy involving Pd-catalyzed silicon-based C(sp2)-C(sp3) cross-coupling. This method allows the modular assembly of a vast array of structurally novel and interesting sila-benzo[b]oxepines with good functional group tolerance. The key to success for this reaction is that silicon atoms have a stronger affinity for oxygen nucleophiles than carbon nucleophiles, and silacyclobutanes (SCBs) have inherent ring-strain-release Lewis acidity.

| S-EPMC8565370 | biostudies-literature

Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones.

Project description:The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles via an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(i) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.

| S-EPMC8159440 | 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