Unprecedented one-pot sequential thiolate substitutions under mild conditions leading to a red emissive BODIPY dye 3,5,8-tris(PhS)-BODIPY

Roacho, Robinson I.; Metta‐Magaña, Alejandro J.; Peña‐Cabrera, Eduardo; Pannell, Keith H.

doi:10.1039/c4ob01892c

Cited by 18 publications

(23 citation statements)

References 47 publications

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“…In contrast, oxygen‐ and sulfur‐based nucleophiles do not lead to product formation under these reaction conditions. However, Pannell et al recently reported a similar methodology in THF, with which the 3,5‐hydrogen atoms of a meso ‐(phenylthio)‐BODIPY could be substituted with thiophenol 24b…”

Section: Functionalization At the 3‐ And 35‐positionsmentioning

confidence: 99%

“…Derivatization at the 8‐position (or meso ‐position) is straightforward when starting from aromatic aldehydes or acylium equivalents 6–8. 8‐MethylthioBODIPYs, introduced by Biellmann et al,91 undergo nucleophilic aromatic substitution (S N Ar) reactions with a variety of nucleophiles 24b,92–98. However, 8‐halogenated (Cl, Br, I) boradiaza‐ s ‐indacenes 106a – c provide an excellent alternative because they can be substituted under mild reaction conditions.…”

Section: Functionalization At the 8‐positionmentioning

confidence: 99%

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Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

2015

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In this review we describe the various new methodologies for synthetic postmodification of the BODIPY core designed and developed by our research groups, as well as their electronic spectroscopic properties. We discuss the different strategies created for functionalization of the BODIPY framework at the pyrrole C‐ring positions and the meso‐position. Halogenated boron dipyrrins are substrates for nucleophilic substitution or Pd‐catalyzed cross‐coupling reactions. α‐Unsubstituted BODIPYs can be functionalized with N and C nucleophiles through oxidative or vicarious nucleophilic substitution (VNS) of the α‐hydrogen atoms. Combining this methodology with reversible Michael addition onto nitrostyrenes provides a route to 3‐styrylated BODIPYs. Furthermore, the one‐step, Pd‐catalyzed C–H arylation of 3,5‐unsubstituted BODIPYs leads to 3‐ and 3,5‐arylated dyes. Finally, radical C–H arylation at the 3,5‐positions of α‐unsubstituted BODIPYs provides an additional synthesis route to arylated dyes.

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Section: Functionalization At the 3‐ And 35‐positionsmentioning

confidence: 99%

Section: Functionalization At the 8‐positionmentioning

confidence: 99%

Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

2015

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“…When DCM is utilized as solvent, the substitution only occurs at the meso-(8)-position, while, as we previously noted, THF promotes a further substitution in the 3-and 5-positions. 16 Emission spectroscopy revealed that the fluorescence intensity for 1-6 decreases as solvent polarity increases, an effect we had previously described in 8-aminoBODIPYs, due to efficient solvation of the polar species facilitating to non-radiative relaxation.…”

Section: Resultsmentioning

confidence: 51%

Formation of 8-RS-BODIPYs via direct substitution of 8-MeS-BODIPY by RSH (R = Et, Pr, Bu, ^tBu, n-C₁₂H₂₅, C₆H₅, p-MeC₆H₄, p-MeOC₆H₄, and 2,6-Me₂C₆H₃)

et al. 2016

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Reactions between 8-RS-BODIPY (R = Me, 1) and alkyl and aryl thiols were readily accomplished in dichloromethane (DCM) to provide a synthetic pathway to a range of new 8-organothioBODIPYs in good yield. The new alkyl 8-RS-BODIPYs, R = Et, 2; Pr, 3; Bu, 4; t Bu, 5, n-Dodecyl, 6; exhibit absorption and emission properties essentially unchanged from those of 1 whereas the arylthio analogs, R = Ph, 7; 2,6-Me 2 C 6 H 3 , 8; p-MeC 6 H 4 , 9; p-MeOC 6 H 4 , 10, exhibit no fluorescence with the exception of 7, and then only in hexane. In common with other related 8-substituted BODIPYs the new 8-alkylthio-BODIPY dyes show decreasing fluorescence intensity as solvent polarity increases. Compounds 2, 3, 7, and 8 were characterized via single crystal X-ray analysis; the alkyl derivatives 2 and 3 exhibited planar BODIPY cores with co-planar organothio-substituents, whereas the aryl derivatives exhibited both BODIPY core deformation and significant twisting about the S-C(8) bond removing co-planarity between the aryl group and the distorted BODIPY core.These deformations coincide with the significantly reduced emission properties.

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“…[8a], [8b], Many of these derivatization methods are based on halogenated BODIPYs or already core‐substituted BODIPYs ,. [8a], α‐Unsubstituted BODIPYs can be functionalized with nucleophiles through oxidative, vicarious, or copper‐catalyzed vicarious nucleophilic substitution of the α‐hydrogen atoms. Dehaen and co‐workers[13b] were the first to report the selective oxidative nucleophilic substitution of the hydrogen atom (ONSH) at the 3‐ and 5‐positions or the α‐position by using CH‐acidic compounds or amines as nucleophiles (Scheme a).…”

Section: Introductionmentioning

confidence: 99%

Sequential Nucleophilic Substitution of the α‐Pyrrole and p‐Aryl Positions of meso‐Pentafluorophenyl‐Substituted BODIPYs

et al. 2017

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Boron–dipyrrins (BODIPYs) have found widespread application in bioimaging and materials science. These applications require the tuning of the chemical and photophysical properties of the fluorophore through the introduction of functional groups at the BODIPY core. In this context, an approach to difunctionalized BODIPYs was explored. Oxidative nucleophilic substitution of hydrogen (ONSH) in the 3‐(α‐)position of the BODIPYs was combined with nucleophilic substitution (SNAr) at the aryl unit of pentafluorophenyl‐substituted BODIPYs and their dipyrrane precursors. In an alternative approach, α‐alkoxy‐substituted BODIPYs were prepared starting from the corresponding dipyrrin. In this case, the α‐methoxy group of the BODIPY was susceptible to a hitherto unreported methoxy/amino exchange. The compounds were investigated with respect to their optical spectroscopic properties, revealing the influence of the different substitution patterns on their absorption and emission spectra.

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Unprecedented one-pot sequential thiolate substitutions under mild conditions leading to a red emissive BODIPY dye 3,5,8-tris(PhS)-BODIPY

Cited by 18 publications

References 47 publications

Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

Formation of 8-RS-BODIPYs via direct substitution of 8-MeS-BODIPY by RSH (R = Et, Pr, Bu, ^tBu, n-C₁₂H₂₅, C₆H₅, p-MeC₆H₄, p-MeOC₆H₄, and 2,6-Me₂C₆H₃)

Sequential Nucleophilic Substitution of the α‐Pyrrole and p‐Aryl Positions of meso‐Pentafluorophenyl‐Substituted BODIPYs

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Unprecedented one-pot sequential thiolate substitutions under mild conditions leading to a red emissive BODIPY dye 3,5,8-tris(PhS)-BODIPY

Cited by 18 publications

References 47 publications

Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

Formation of 8-RS-BODIPYs via direct substitution of 8-MeS-BODIPY by RSH (R = Et, Pr, Bu, tBu, n-C12H25, C6H5, p-MeC6H4, p-MeOC6H4, and 2,6-Me2C6H3)

Sequential Nucleophilic Substitution of the α‐Pyrrole and p‐Aryl Positions of meso‐Pentafluorophenyl‐Substituted BODIPYs

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Formation of 8-RS-BODIPYs via direct substitution of 8-MeS-BODIPY by RSH (R = Et, Pr, Bu, ^tBu, n-C₁₂H₂₅, C₆H₅, p-MeC₆H₄, p-MeOC₆H₄, and 2,6-Me₂C₆H₃)