Phase-transfer-catalyst enabled enantioselective C–N coupling to access chiral boron-stereogenic BODIPYs

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

Опубликована: Март 19, 2025

Tetracoordinate boron-based fluorescent materials have shown extensively applications in chemistry, biology and science owing to their unique optoelectronic properties. However, constructing chiral boron-stereogenic fluorophores through practical universal strategies remains rare challenging. Herein, as a proof of concept, we report an enantioselective postfunctionalization boron dipyrromethene dyes (BODIPYs), acess BODIPYs moderate good yields with commendable enantioselectivity. Chiral attracted increasing attention not only distinctively photophysical properties circularly polarized luminescence (CPL) materials, but also diversely structural modification. In this·work, present phase-transfer-catalyst enabled C–N coupling reaction diverse nucleophiles. This method serves SNAr (nucleophilic aromatic substitution reaction) route achieve series amido/amino well demonstrates promising CD and·CPL·activities, excellent biocompatibility, high specificities, showing potential imaging agents. Constructing Here, the authors

Язык: Английский

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Organocatalyzed Enantioselective C–N Bond-Forming S_NAr Reactions for Synthesizing Stereogenic-at-Boron BODIPYs

JACS Au, Год журнала: 2025, Номер 5(4), С. 1965 - 1973

Опубликована: Апрель 2, 2025

The precise construction of boron stereogenic centers represents a significant, yet challenging frontier in asymmetric catalysis, garnering growing attention recent years. However, feasible catalysis has primarily been limited to transition-metal-catalyzed desymmetrization pro-chiral BODIPY molecules, while enantioselective synthesis via organocatalysis remains unexplored. Herein, we achieve an organocatalyzed C-N bond-forming SNAr reaction 3,5-dihalogen BODIPYs phase-transfer enabling the efficient broad range boron-stereogenic with excellent enantioselectivities (>40 examples, up 99% ee). significance and potential this catalytic approach are further underscored by versatile applications enantioenriched 3-amide synthesis, optical activity regulation, bioimaging, sensing, promoting development fluorophores.

Язык: Английский

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Recent Advances of Boron‐Containing Chiral Luminescent Materials^†

Chinese Journal of Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 25, 2024

Comprehensive Summary As a class of organic dyes, boron‐containing compounds play an important role in luminescent materials. They have attracted considerable attention due to their unique photophysical properties. Chiral systems wide range practical applications biological imaging, optoelectronic devices, information storage and 3D display. Boron‐containing chiral materials can not only effectively improve the properties CPL materials, but also bring system, which enables them be used as favorable emitting for expanded applications. Here, we review research progress by detailed discuss according different skeletons, such point chirality, 1,1’‐binaphthyl, [ n ]helicenes, [2,2]paracyclophane pillar[5]arenes. We believe that this is significance development Key Scientists The studies circularly polarized luminescence (CPL) based on small molecules advanced significantly. However, gained recent years. In 2019, Zhao's group prepared binaphthalene derivative modified with triarylborane, representing molecule material exhibit characteristics responsive both solvent fluoride ions. 2020, Chen's steric effects triarylborane triphenylamine prepare planar 2021, Wang's developed new B,N‐embedded double hetero[7]helicenes strong chiroptical responses UV‐visible region. same year, He's asymmetric reactions synthesize boron‐based point‐chirality high efficiency enantioselectivity. 2023, Ravat synthesized 1,4‐B,N‐embedded helicenes exhibiting narrow‐band fluorescence CPL. During period, Matthias Wagner et al obtained (BO) 2 ‐doped tetrathia[7]helicene via efficient four‐step synthesis, Zheng reported nearly pure green electroluminescent device (CP‐OLED). 2024, hetero‐[9]helicenes offering pathway towards significantly enhanced helicene‐based CPEL.

Язык: Английский

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Asymmetric and Symmetric S-zig-zag-Fused BODIPYs: Synthesis and Photophysical and Oxidative Properties

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 18, 2025

We present a new, straightforward, and versatile approach that utilizes regioselective brominated precursors to synthesize both asymmetric symmetric S-zig-zag-fused BODIPYs (s-TFB bis-TFB) in moderate yields (45% 40%, respectively). X-ray structure analyses reveal the planar rigidity of BODIPY skeleton is progressively enhanced with an increasing number thiopyran rings. The annulation S-heteroaromatic rings at zig-zag edge core results blue-shifted absorption emission spectra, bis-TFB exhibiting maxima 530 539 nm elevated LUMO energy levels. In contrast, oxidation s-TFB m-CPBA demonstrates significant site selectivity, affording four products, namely s-s-SFB, s-bis-SFB, bis-s-SFB, bis-bis-SFB, ranging from 22% 36%. These oxidated derivatives display large red-shifted spectra (e.g., 648 735 for s-bis-SFB), along more stable HOMO levels reduced HOMO-LUMO gaps. This cyclization/oxidation strategy enables precise tuning optoelectronic properties, opening new avenues dye design application.

Язык: Английский

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Enabling Construction of Boron-Stereogenic Formyl BODIPYs via N-Heterocyclic Carbene-Catalyzed Enantioselective Esterification

JACS Au, Год журнала: 2025, Номер unknown

Опубликована: Май 16, 2025

Язык: Английский

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Oxa-phenalene [b]-fused BODIPY Dyes: Synthesis, Structures, and Photophysical Properties

Tetrahedron, Год журнала: 2025, Номер unknown, С. 134728 - 134728

Опубликована: Май 1, 2025

Язык: Английский

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Fully Conjugated Thiophene-Fused Oligo-BODIPYs: A Class of Intensely Near-Infrared Absorbing, Arc-Shaped Materials with up to 31 Linearly-Fused Rings

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 28, 2025

Structurally well-defined large π-conjugated systems attract significant interest in molecular materials both for their unique electronic/photophysical properties and unexplored structure-property relationships arising from synthetic challenges. Herein, we address this challenge by leveraging a series of polycondensed π-system doping with B, N S heteroatoms. In our approach, fully conjugated thiophene-fused oligo-BODIPYs atomic precision have been efficiently synthesized through the combination intermolecular SNAr reactions followed intramolecular aromatic oxidative couplings halogenated BODIPY precursors. The largest architecture is fused octamer, featuring coplanar backbone 31 linearly rings. extended π-conjugation causes dramatic shift absorption event about 500 nm (monomer) to 822 (octamer) extremely high molar absorptivities reaching 800,000 M-1 cm-1, as well maintaining intense fluorescence intensity (ΦFL up 0.32), long triplet lifetime (τT = 0.61-15.4 μs), efficient quantum yields (ΦT 0.24-0.81) good singlet oxygen generation abilities. More interestingly, due weak aromaticity thiophene, exhibit state localization conjugation length increases, where energy remains constant while decreases significantly. Notably, near-infrared thermally activated delayed (TADF) observed even tetramers, hexamers, octamers. Our findings not only present new heteroatom-doped condensed π-systems but also establish precise regulation mechanism singlet-triplet levels molecules rigid structures. Furthermore, work provides novel strategy designing next-generation TADF narrowband emission.

Язык: Английский

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Synthesis of BODIPY Oligomers Via Post‐Functionalization

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(41)

Опубликована: Июль 24, 2024

Abstract Synthesis of BODIPY oligomers has attracted increasing attention due to their intriguing properties and promising applications. Significant progress been made synthesize via post‐functionalization, either single‐bond linked or fully conjugated. This concept article highlights the recent developments oligomers, including synthetic routes, photophysical applications in areas NIR light absorbing dye, photodynamic therapy, bioimaging etc.

Язык: Английский

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BODIPY: synthesis, modification, and applications in sensing and biomedicine

Russian Chemical Reviews, Год журнала: 2024, Номер 93(10), С. RCR5136 - RCR5136

Опубликована: Окт. 1, 2024

BODIPY chromophores (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) are one of the most versatile fluorophores which commonly used in a variety scientific fields. The combination excellent photophysical properties with possibility easy chemical modification structure, and photostability determines application biomedicine, photocatalysis, analytical chemistry materials science. This review summarizes approaches to synthesis BODIPY, discussing both classical recently-published synthetic postfunctionalization approaches. An influence structure various methods on their potential applications science biosensorics also discussed.<br> bibliography includes 344 references.

Язык: Английский

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Multicomponent Diversity-Oriented Access to Boronic-Acid-Derived Pyrrolide Salicyl-Hydrazone Fluorophores with Strong Solid-State Emission

Inorganic Chemistry, Год журнала: 2024, Номер 63(45), С. 21397 - 21409

Опубликована: Окт. 31, 2024

Fluorescent molecular platforms are highly sought after for their applications in biology and optoelectronics but face challenges with solid-state emission quenching. To address this, bulky substituents or aggregation-induced luminogens to restrict intramolecular motion used enhance the brightness. Here, we have successfully engineered a novel class of boron complexed pyrrolide salicyl-hydrazone fluorophores named BPSHY. These dyes were synthesized through diversity-oriented condensation pyrrole salicylaldehyde derivatives combined various aromatic boronic acids. The resulting 3D structures, owing axially substituted aryl groups, impart excellent solubility variety solvents. Significantly, BPSHY exhibit strong absorption visible region remarkably large Stokes shifts. Crucially, they demonstrate intense aqueous solutions due effects. In solid-states, these achieve high quantum yields, reaching up 58%. Further expanding utility, developed two new probes: one incorporating morpholine another containing triphenylphosphine salt. Both them found specifically label subcellular organelles such as lysosomes mitochondria within live cells. Notably, probes exceptional staining efficacy two-photon fluorescence feature. This highlights considerable promise monitoring visualizing dynamic transformations organelles.

Язык: Английский

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