Synthesis and regioselective functionalization of perhalogenated BODIPYs

Zhao, Ning; Xuan, Sunting; Byrd, Brandon R.; Fronczek, Frank R.; Vicente, M. Graça H.

doi:10.1039/c6ob00935b

Cited by 29 publications

(27 citation statements)

References 48 publications

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“…13, 16 The results from reactivity investigations showed the following orders of reactivity for Pd(0)-catalyzed Stille cross-coupling reactions: 16 8-Cl ≈ 1,7-Br > 3,5-Cl > 2,6-Cl, and for nucleophilic substitution reactions: 5a, 16b, 16c 8-Cl > 3,5-Cl > 2,6-Cl. Based on these studies, the perhalogenated BODIPY 1 was chosen as the starting material.…”

Section: Resultsmentioning

confidence: 99%

“…Based on these studies, the perhalogenated BODIPY 1 was chosen as the starting material. 13 Treatment of BODIPY 1 with 2 equivalents of phenol, in the presence of potassium carbonate, in refluxing CH 2 Cl 2 , yielded the 8-phenoxy BODIPY 2 as the major product in 53% isolated yield, along with the 3,8-diphenoxy BODIPY as a minor product. By increasing the nucleophile stoichiometry to 10 equivalents, the 3,5,8-tri-substituted BODIPY 3 was the only product isolated in high yield (89%), as shown in Scheme 1.…”

Section: Resultsmentioning

confidence: 99%

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Enhanced Hypsochromic Shifts, Quantum Yield, and π–π Interactions in a meso,β-Heteroaryl-Fused BODIPY

et al. 2017

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We report the synthesis and investigation of an unprecedented 8-heteroaryl-fused BODIPY 4. This compound exhibits enhanced π-π stacking in the solid state, unusually large blue-shifts in the absorbance and emission spectra, and higher quantum yield than its unfused precursor; DFT calculations suggest a small energy gap for 4, and strong electronic communication between the 8-OPh and the BODIPY core.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Enhanced Hypsochromic Shifts, Quantum Yield, and π–π Interactions in a meso,β-Heteroaryl-Fused BODIPY

et al. 2017

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“…The introduction of phenyl groups at the 2,6-positions, as in BODIPY 4 , further induced bathochromic shifts of 18–20 nm for absorption and 19–28 nm for emission relative to 2 ; larger red-shifts were observed upon introduction of electron-donating thienyl groups at the 2,6-positions, in the order of 54–56 nm for absorption and 77–95 nm for emission, as previously observed. 13a, 18 …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Spectroscopic Investigation of a Series of Push–Pull Boron Dipyrromethenes (BODIPYs)

Xuan

Zhao

et al. 2017

J. Org. Chem.

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A series of push-pull BODIPYs bearing multiple electron-donating and electron-acceptor groups were synthesized regioselectively from 2,3,5,6,8-pentachloro-BODIPY, and characterized by NMR spectroscopy, HRMS and X-ray crystallography. The influence of the push-pull substituents on the spectroscopic and electrochemical properties of BODIPYs was investigated. Bathochromic shifts were observed for both absorbance (up to 37 nm) and emission (up to 60 nm) in different solvents upon introduction of the push-pull moieties. DFT calculations, consistent with the spectroscopic and cyclic voltammetry studies, show decreased HOMO-LUMO energy gaps upon the installation of the push-pull moieties. BODIPY 7 bearing thienyl groups on the 2 and 6 positions showed the largest λmax for both absorption (635–653 nm) and emission (706–707 nm), but also the lowest fluorescence quantum yields. All BODIPYs were non-toxic in the dark (IC50 > 200 μM) and showed low phototoxicity (IC50 > 100 μM, 1.5 J/cm2) toward human HEp2 cells. Despite the relatively low fluorescence quantum yields, the push-pull BODIPYS were effective for cell imaging, readily accumulating within cells and localizing mainly in the ER and Golgi. Our structure-property studies can guide future design of functionalized BODIPYs for various applications, including bioimaging and in dye-sensitized solar cells.

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“…The halogenation of BODIPYs is one of the most important transformations as it leads to compounds that are sufficiently stable to be isolated, but amenable towards a range of nucleophilic displacement and metal‐catalysed coupling reactions . Chlorination was studied with dimesityl derivative 1 .…”

Section: Resultsmentioning

confidence: 99%

One‐Pot Preparation of Non‐Symmetric meso‐Aryl‐BODIPYs: Functional Derivatives with Unusual Reactivity

et al. 2016

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The formation of meso‐aryl‐BODIPYs (boron dipyrrins) through the acidic condensation of 3,4‐dialkylpyrroles with aromatic aldehydes, followed by 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) oxidation and BF2 complexation, has been reviewed. Surprisingly, it was found that the major products from these reactions were not the anticipated symmetric BODIPYs, but non‐symmetric derivatives carrying one benzyl substituent at the BODIPY α position. The best yields and simple purification conditions were be achieved if the oxidant was not employed in the one‐pot reaction sequence. Electron‐rich benzaldehydes provided the best results, whereas precursors with electron‐withdrawing substituents gave significant amounts of the symmetric BODIPYs as side‐products. This unexpected result can be rationalized mechanistically on the basis of two reaction pathways that diverge from a common intermediate at an early step in the condensation sequence. Preliminary reactivity investigations showed chlorination to give unexpected results, but a typical substitution and coupling chemistry.

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Synthesis and regioselective functionalization of perhalogenated BODIPYs

Cited by 29 publications

References 48 publications

Enhanced Hypsochromic Shifts, Quantum Yield, and π–π Interactions in a meso,β-Heteroaryl-Fused BODIPY

Enhanced Hypsochromic Shifts, Quantum Yield, and π–π Interactions in a meso,β-Heteroaryl-Fused BODIPY

Synthesis and Spectroscopic Investigation of a Series of Push–Pull Boron Dipyrromethenes (BODIPYs)

One‐Pot Preparation of Non‐Symmetric meso‐Aryl‐BODIPYs: Functional Derivatives with Unusual Reactivity

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