Organocatalytic Atroposelective Fluorooxindole Addition to Coumarin Michael Acceptors

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Organocatalytic atropisomeric synthesis with fluorinated oxindoles and 4-halo-3-nitrocoumarins gives congested structures displaying a Csp2-Csp3 chirality axis an adjacent tetrasubstituted stereogenic carbon center good yields, up to 97% ee 41 : 1 dr. The scalable dehalogenative C-C bond formation is achieved under mild conditions commercially available urea catalyst.

Язык: Английский

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Catalytic Asymmetric Synthesis of Unnatural Axially Chiral Biaryl δ‐Amino Acid Derivatives via a Chiral Phenanthroline‐Potassium Catalyst‐Enabled Dynamic Kinetic Resolution

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 15, 2024

Axially chiral biaryl δ-amino acids possess significantly different conformational properties and environment from centrally amino acids, therefore, have drawn considerable attention in the fields of synthetic medicinal chemistry. Herein, a novel phenanthroline-potassium catalyst has been developed by constructing well-organized axially ligand composed one 1,10-phenanthroline unit two 1,1'-bi-2-naphthol (BINOL) units. In presence this catalyst, good to excellent yields enantioselectivities (up 99 % yield, 98 : 2 er) achieved ring-opening alcoholytic dynamic kinetic resolution variety lactams, thereby providing an efficient protocol for catalytic asymmetric synthesis unnatural acid derivatives.

Язык: Английский

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Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 30, 2025

Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where is exclusively attributed to the metal center due specific coordination pattern of achiral ligands around ion, broadly utilized in diverse areas natural science. However, synthesis these molecules remains constrained. Notably, while asymmetric catalysis played a crucial role production optically active organic molecules, its application less straightforward. In this study, we introduce kinetic resolution strategy employing Pd-catalyzed Suzuki-Miyaura cross-coupling reaction that efficiently produces stereogenic-at-iridium from racemic mixtures with high selectivity (achieving an s-factor up 133). This method enables further relevant chiral metallodrugs photosensitizers, underscoring practical utility our approach. Mechanistic studies suggest reductive elimination likely turnover-limiting step cross-coupling.

Язык: Английский

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Enantioselective construction of inherently chiral pillar[5]arenes via palladium-catalysed Suzuki–Miyaura cross-coupling

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 10, 2025

Pillar[n]arenes have broad applications in biological medicine, materials science, and supramolecular gels. Notably, enantiopure pillar[5]arenes are valued for their roles enantioselective host–guest recognition, chiral sensing, asymmetric catalysis, related fields. Current methods obtaining pillar[n]arenes rely heavily on resolution agents or HPLC resolution. However, the synthesis of these compounds via catalysis remains challenging. In this study, we develop an extended side-arm Suzuki–Miyaura cross-coupling strategy to construct inherently with excellent yields high enantioselectivities using a palladium catalyst Sadphos ligand. The reaction scope extends beyond arylboronic acids encompass 2-arylvinylboronic other multi-OTf-substituted substrates, all efficiently producing desired products. Further exploration synthetic applications, along photophysical chiroptical analyses, confirm potential diverse across multiple disciplines. Enantiopure recognition but current Here, authors pillar[5]arenes.

Язык: Английский

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Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(28)

Опубликована: Май 16, 2024

Abstract Axially chiral biaryl scaffolds are important in pharmaceuticals, natural products, and asymmetric synthesis. Atroposelective ring‐opening of configurationally labile reagents via dynamic kinetic transformation provides a valuable approach to access axially atropisomers. This review summarizes seminal contributions recent advancements on this topic based the use different types reagents.

Язык: Английский

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Directing group controlled regioselective C–H borylation of 2-arylphenolic compounds at room temperature

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(15), С. 4249 - 4257

Опубликована: Янв. 1, 2024

The Fe(OTf) 3 -promoted directing group-controlled regioselective C–H borylation of 2-arylarenolic compounds was achieved at room temperature, affording two useful arylboronic acids efficiently.

Язык: Английский

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Symmetric Anion Mediated Dynamic Kinetic Asymmetric Knoevenagel Reaction for N−C and N−N Atropisomers Synthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 21, 2024

A symmetric anion mediated dynamic kinetic asymmetric Knoevenagel reaction was established as a general and efficient method for accessing both N-C N-N atropisomers. The resulting highly enantio-pure pyridine-2,6(1H,3H)-diones exhibit diverse structures functional groups. key to excellent regio- remote enantiocontrol could be owed the hydrogen bond between enolate triflamide block of organocatalyst. This connected iminium cation by chiral backbone. mechanism investigation via control experiments, correlation analysis, density theory calculations further revealed how stereochemical information transferred from catalyst into axially pyridine-2,6(1H,3H)-diones. synthetic applications also demonstrated reaction's potential.

Язык: Английский

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Divergent Synthesis of Chiroptical Molecular Switches Based on 1,2-Diaxial Atropisomers

JACS Au, Год журнала: 2024, Номер 4(11), С. 4445 - 4454

Опубликована: Окт. 14, 2024

The development of chiroptical molecular switches for chiral sensing, data communication, optical displays, logic gates, and asymmetric catalysis is currently a vibrant frontier science technology. Herein, we report practical artificial dynamic system based on 1,2-diaxial atropisomer. Organocatalytic parallel kinetic resolution allows the divergent synthesis two sets stereoisomers with vicinal C-C N-N axes from same racemic single-axis substrates. By simply varying configuration single catalyst, all four are accessible. successive conduction covalent unlocking/locking thermal-isomerization processes enables sequential switching between atropisomeric states electronic circular dichroism signal reversal, providing an example multistate switches.

Язык: Английский

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Access to Axially Chiral Biaryl Benzylamines via Ancestral Enzyme-Enabled Reductive Amination Desymmetrization

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1522 - 1531

Опубликована: Янв. 11, 2025

Axially chiral biaryl benzylamines are present in numerous natural products, pharmaceuticals, ligands, and catalysts. However, the direct catalytic synthesis of these functional molecules using a robust strategy remains formidable challenge. Reductive amination desymmetrization dialdehydes offers powerful approach for construction axially but suffers from extensive undesirable side reactions. Herein, we engineered ancestral imine reductases to enable reductive dialdehydes, allowing wide range with up 99% conversion enantiomeric excess (ee). The ratio product byproducts was 97:3 over 90:10 most cases. This work presents an alternative accessing will stimulate development associated bioactive catalysts/ligands.

Язык: Английский

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NHC and photoredox co-catalyzed 1,4-alkylcarbonylation of 1,3-enynes

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A strategy to obtain 1,2-alkenyl ketone products by radical relay coupling is proposed.

Язык: Английский

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