Beyond conventional: Role of chiral metal–organic frameworks in asymmetric scenarios

Nano Today, Год журнала: 2024, Номер 56, С. 102227 - 102227

Опубликована: Март 18, 2024

Язык: Английский

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Catalytic asymmetric C–N cross-coupling towards boron-stereogenic 3-amino-BODIPYs

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

Опубликована: Янв. 7, 2025

3-Amino boron dipyrromethenes (BODIPYs) are a versatile class of fluorophores widely utilized in live cell imaging, photodynamic therapy, and fluorescent materials science. Despite the growing demand for optically active BODIPYs, synthesis chiral 3-amino-BODIPYs, particularly catalytic asymmetric version, remains challenge. Herein, we report boron-stereogenic 3-amino-BODIPYs via palladium-catalyzed desymmetric C–N cross-coupling prochiral 3,5-dihalogen-BODIPYs. This approach features broad substrate scope, excellent functional group tolerance, high efficiency, remarkable enantioselectivities, under mild reaction conditions. Further stereospecific formation 3,5-diamino-BODIPYs, along with an investigation into photophysical properties resulting optical BODIPYs also explored. protocol not only enriches chemical space chiroptical BODIPY dyes but contributes to realm chemistry. (BODIPYs), which useful science, authors first cross-couplings.

Язык: Английский

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Enantioselective Construction of Quaternary Stereocenters via A Chiral Spiro Phosphoric Acid-Assisted Formal Gold Carbene gem-Dialkylation Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19261 - 19270

Опубликована: Июль 1, 2024

Enantioselective construction of all-carbon quaternary stereocenters has attracted much attention over the past few decades. A variety catalytic asymmetric methods have been disclosed based on use presynthesized complex reagents that impart congested steric hindrance to reaction center, which generally produce chiral molecules through forming one C-C bond. The readily available could build two bonds same carbonic center with concomitant assembly remains challenging. Herein, we disclose a alkyne multifunctionalization using gold and spiro phosphoric acid (SPA) for synergistic catalysis. In this method, accessible internal alkynes served as key carbene precursors, followed by

Язык: Английский

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Transition-metal-catalyzed enantioselective C–N cross-coupling

Chemical Society Reviews, Год журнала: 2024, Номер 53(19), С. 9560 - 9581

Опубликована: Янв. 1, 2024

Chiral amine scaffolds are among the most important building blocks in natural products, drug molecules, and functional materials, which have prompted chemists to focus more on their synthesis. Among accomplishments chiral synthesis, transition-metal-catalyzed enantioselective C-N cross-coupling is considered one of efficient protocols. This approach combines traditional C(sp

Язык: Английский

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Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling

Chem, Год журнала: 2024, Номер 10(11), С. 3323 - 3341

Опубликована: Июль 5, 2024

Cavitands have emerged as privileged architectures in supramolecular chemistry. Nonetheless, achieving structural diversity and tunability through heterofunctionalization along the rims of macrocycles has remained a formidable challenge. As rudimental example, stepwise conversion C4v-symmetric scaffolds to inherently chiral ABCD patterns is synthetically impractical owing low theoretical yields (0.8%) need for chromatographic enantioseparation.Herein, we report catalytic desymmetrization strategy access cavitands. Through engineering ionic palladium catalysts, diverse functionalities, including aryl, alkenyl, alkynyl, amino groups, can be installed on large with high site- stereoselectivity. An adaptable protocol been established furnish designer ABCD-type cavitands accordance choreography coupling partners. Experimental computational studies reveal synergistic electrostatic steering catalysis by catalyst–substrate interactions.

Язык: Английский

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sSPhos: A General Ligand for Enantioselective Arylative Phenol Dearomatization via Electrostatically-Directed Palladium Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(47), С. 25553 - 25558

Опубликована: Ноя. 16, 2023

Arylative phenol dearomatization affords complex, cyclohexanone-based scaffolds from simple starting materials, and asymmetric versions allow access to valuable enantioenriched structures. However, bespoke chiral ligands must typically be identified for each new scaffold variation. We have addressed this limitation by applying the concept of electrostatically-directed palladium catalysis whereby sulfonated ligand sSPhos engages in electrostatic interactions with a phenolate substrate via its associated alkali metal cation. This approach allows highly spirocyclohexadienones, process originally reported Buchwald co-workers predominantly racemic manner. In addition, is proficient at forming two other distinct scaffolds, which had previously required fundamentally different ligands, as well novel oxygen-linked scaffold. envisage that broad generality displayed will facilitate expansion important reaction type highlight potential unusual design principle, harnesses attractive interactions.

Язык: Английский

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Engineered enzymes for enantioselective nucleophilic aromatic substitutions

Nature, Год журнала: 2025, Номер unknown

Опубликована: Янв. 15, 2025

Язык: Английский

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Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Язык: Английский

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Palladium-catalyzed enantioselective β-hydride elimination for the construction of remote stereocenters

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

Опубликована: Март 5, 2025

The β-H elimination is a crucial elementary step in transition-metal catalysis, but controlling the stereochemistry of this process has been underdeveloped. limited works reported so far have only focused on creating axial chirality allenes, and no report able to build central using asymmetric elimination. In study, we Trost ligand-enabled enantioselective desymmetric reaction from π-allyl-Pd. This transformation provides rapid access cyclohexenes bearing C4-remoted stereocenter, total synthesis (-)-oleuropeic acid (-)-7-hydroxyterpineol demonstrated. Computational studies shown that rate-determining step, non-covalent interactions between amide moiety ligand benzene cyclohexane moieties substrate play key role stereocontrol during

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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