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

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 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.

Language: Английский

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

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 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

Language: Английский

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Modular enantioselective assembly of multi-substituted boron-stereogenic BODIPYs

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 83 - 91

Published: Sept. 20, 2024

Language: Английский

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Boron‐Stereogenic Compounds: Synthetic Developments and Opportunities

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(19), P. 2401 - 2411

Published: May 27, 2024

Comprehensive Summary The 21 st century has witnessed a continuous evolution in the development of boron‐stereogenic chemistry. Since 1990s, various innovations for synthesis tetracoordinate compounds, which exhibited great potential applications, have been demonstrated by synthetic chemists. This paper reviews significant progress and recent advances towards assembly enantioenriched hopes to shed light on new perspectives inspire further research this emerging field.

Language: Английский

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Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C‐H (Hetero)Arylation with Diazonaphthoquinones and Diazoindenines

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis structurally diverse boron-stereogenic BODIPYs through intermolecular desymmetrization and with atroposelectivity remains elusive. Here, we showcase rhodium(II)-catalyzed site-specific C-H (hetero)arylations prochiral polysubstituted diazonaphthoquinonesand diazoindenines, providing efficient pathways the rapid assembly versatile (hetero)arylated axially chiral long-range axial rotational restriction modes. synthetic application procedures been emphasized by BODIPY derivatives various functions. Photophysical properties, bioimaging, lipid droplet-specific targeting capability are also demonstrated, indicating promising applications in biomedical research, medicinal chemistry, material science.

Language: Английский

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Synthesis of chiral boranes via asymmetric insertion of carbenes into B-H bonds catalyzed by the rhodium(I) diene complex

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(65), P. 8601 - 8604

Published: Jan. 1, 2024

Catalytic insertion of diazo compounds into B–H bonds produces unique with tetrahedral chiral boron atoms.

Language: Английский

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Recent Advances in the Development of Enantiopure BODIPYs and Some Related Enantiomeric Compounds

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

During the process of developing smart chiroptical luminophores, BODIPYs have emerged as candidates utmost importance. Here in we will discuss their synthesis.

Language: Английский

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Structure-Property/Activity Correlations of Coordination Compounds, Supramolecular Molecular Assemblies and Materials, with Possible Industrial and Biological Applications

Journal of the Mexican Chemical Society, Journal Year: 2025, Volume and Issue: 69(1), P. 123 - 151

Published: Jan. 1, 2025

This work gives an overview of the scientific contributions developed in research group prof. Dr. Hiram Isaac Beltrán during last 22 years his career, mainly at Universidad Autónoma Metropolitana, first Unidad Cuajimalpa and later Azcapotzalco. During this period, was carried out on development of, (i) organic ligands to obtain boron-coordination compounds, (ii) diorganotin(IV) coordination compounds directly obtained by template effect, (iii) applications lines derived from boron tin, (iv) polymers metal-organic frameworks (MOFs), (v) infiltrated MOFs, (vi) band gap modulation luminescence properties (vii) biological (viii) macrocyclic systems their applications, (ix) supramolecular assemblies applications. Conducting more than 90 papers about 20 patents period. All involved design a specific molecular or material system with precise physicochemical achieve goal, fulfill function even be (multi)functional for biologic, industrial purposes. To follow all these directions, some concepts will highlighted compendium presented. Acquiring knowledge experience has allowed us develop functions also helped other groups understand own under investigation furthered field applied chemistry multifunctional level. Resumen. Este trabajo ofrece una visión general de las contribuciones científicas desarrolladas en el grupo investigación del durante los últimos años su carrera, principalmente la primero y luego Durante este periodo, se ha investigado desarrollo ligandos orgánicos para obtención compuestos coordinación con boro, diorganoestaño(IV) obtenidos directamente por efecto templado, aplicaciones líneas derivadas boro estaño desarrollados, polímeros redes metal-orgánicas (MOF), infiltración modulación banda prohibida propiedades luminiscencia (vii ) biológicas sistemas macrocíclicos sus aplicaciones, ensambles supramoleculares aplicaciones.. Realizando más artículos alrededor patentes periodo. Toda esta involucra diseño un sistema o particular fisicoquímicas precisas lograr objetivo, eventualmente cumplir función incluso ser (multi)funcional fines biológicos, científicos industriales. Para seguir todas estas investigación, destacaron algunos conceptos posteriormente presentó compendio. La adquisición conocimiento experiencia permitido diseñar desarrollar moleculares materiales funciones específicas. Esto también ayudado otros grupos comprender propios estudio impulsado campo química aplicada nivel multifuncional.

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Supramolecular‐Assembly and Surfactant‐Regulated Circularly Polarized Luminescence from a Spiranic BINOL‐Derived Borate Isoindolyl‐Indolenine (BBI) Dye

Advanced Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 4, 2025

Abstract Circularly polarized luminescence (CPL) materials have attracted significant attention owing to their unique luminescent properties and broad range of applications. However, challenges remain, including controlling helical assembly, mitigating aggregation‐caused quenching, balancing quantum yield ( Φ PL ) with g values. Here, the study reports synthesis a novel asymmetric, spiranic O‐organoboranes bearing isoindolyl‐indolenine scaffold (BBI) axial chirality through BINOL substitution, as well its supramolecular assembly surfactant‐regulated tunable CPL behaviors. The newly designed BBI dye shows relative weak 10% in toluene. Supramolecular acetonitrile/water co‐solvents exhibit an obvious aggregation‐induced emission (AIE) process, leading formation spherical nanostructures red‐shifted orange‐yellow (554 nm, = 0.012, 7%). Moreover, surfactant sodium dodecyl sulfonate (SDS) can promote aggregation pure deionized water, producing nanofibers blue‐shifted yellow (536 0.006, 13%). Crystal growth toluene/hexane SDS aqueous/acetonitrile systems reveals chiral crystals P 212121 space group, offering insights into amplification. This demonstrates ability precisely control parameters, X‐ray single‐crystal analysis providing additional understanding regulation.

Language: Английский

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Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C‐H (Hetero)Arylation with Diazonaphthoquinones and Diazoindenines

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis structurally diverse boron‐stereogenic BODIPYs through intermolecular desymmetrization and with atroposelectivity remains elusive. Here, we showcase rhodium(II)‐catalyzed site‐specific C−H (hetero)arylations prochiral polysubstituted diazonaphthoquinonesand diazoindenines, providing efficient pathways the rapid assembly versatile (hetero)arylated axially chiral long‐range axial rotational restriction modes. synthetic application procedures been emphasized by BODIPY derivatives various functions. Photophysical properties, bioimaging, lipid droplet‐specific targeting capability are also demonstrated, indicating promising applications in biomedical research, medicinal chemistry, material science.

Language: Английский

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