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

JACS Au, Journal Year: 2025, Volume and Issue: 5(4), P. 1965 - 1973

Published: April 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.

Language: Английский

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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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BODIPY-Doped Nanohoops In and Out of Conjugation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 5, 2025

By combining the well-known motifs of BODIPY dyes and cycloparaphenylenes, novel nanohoop derivatives were accessible via established procedures. Absorption emission spectra showed overall bathochromic shifts, their photophysical behavior can be tuned by introducing steric demand to modulate conjugation throughout system. 19F NMR underline distinct differences in conformations, (TD)DFT calculations provide a deeper insight into geometry, behavior, influence demand.

Language: Английский

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Iridium-Catalyzed Asymmetric Allylic Substitution with Sequential Boron Incorporation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

An iridium-catalyzed asymmetric allylic substitution with sequential boron incorporation is reported. The reaction accommodates a wide range of substrates, affording chiral N,O-bidentate difluoroboron complexes in excellent yields high enantioselectivities. Furthermore, decigram-scale reaction, synthetic transformations, as well photophysical property investigations the are explored.

Language: Английский

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

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: May 16, 2025

Language: Английский

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