Boron Asymmetry in a BODIPY Derivative

Haefelé, Alexandre; Zedde, Chantal; Retailleau, Pascal; Ulrich, Gilles; Ziessel, Raymond

doi:10.1021/ol100109j

Cited by 90 publications

(48 citation statements)

References 36 publications

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“…The 3-methyl group of BODIPY 6c was also regioselectively oxidized in the presence of DDQ [26] giving formyl-BODIPY 17 in 26% yield. Formyl-BODIPYs are useful materials with potential applications as fluorescent sensors, [27] and have been shown to undergo Wittig reactions with alkyl or aryl ylides, [28a] as well as condensations with malononitrile, methyl acetoacetate, [28b] and pyrrole [28c] to produce further functionalized compounds.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of 3,8‐Dichloro‐6‐ethyl‐1,2,5,7‐tetramethyl–BODIPY from an Asymmetric Dipyrroketone and Reactivity Studies at the 3,5,8‐Positions

Zhao

Vicente

Fronczek

et al. 2015

Chemistry A European J

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The asymmetric BODIPY 1a (BODIPY=4,4-difluoro-4-bora-3a,4a-diaza-s-indacene), containing two chloro substituents at the 3,8-positions and a reactive 5-methyl group, was synthesized from the asymmetric dipyrroketone 3, which was readily obtained from available pyrrole 2a. The reactivity of 3,8-dichloro-6-ethyl-1,2,5,7-tetramethyl-BODIPY 1a was investigated by using four types of reactions. This versatile BODIPY undergoes regioselective Pd0-catalyzed Stille coupling reactions and/or regioselective nucleophilic addition/elimination reactions, first at the 8-chloro and then at the 3-chloro group, using a variety of organostannanes and N-, O-, and S-centered nucleophiles. On the other hand, the more reactive 5-methyl group undergoes regioselective Knoevenagel condensation with an aryl aldehyde to produce a monostyryl-BODIPY, and oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) gives the corresponding 5-formyl-BODIPY. Investigation of the reactivity of asymmetric BODIPY 1a led to the preparation of a variety of functionalized BODIPYs with λmax of absorption and emission in the ranges 487–587 and 521–617 nm, respectively. The longest absorbing/emitting compound was the monostyryl-BODIPY 16, and the largest Stokes shift (49 nm) and fluorescence quantum yield (0.94) were measured for 5-thienyl-8-phenoxy-BODIPY 15. The structural properties (including 16 X-ray structures) of the new series of BODIPYs were investigated.

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Section: Resultsmentioning

confidence: 99%

“…The lower quantum yield determined for 17 relative to 6c is in agreement with previous reports. [26] …”

Section: Resultsmentioning

confidence: 99%

Synthesis of 3,8‐Dichloro‐6‐ethyl‐1,2,5,7‐tetramethyl–BODIPY from an Asymmetric Dipyrroketone and Reactivity Studies at the 3,5,8‐Positions

Zhao

Vicente

Fronczek

et al. 2015

Chemistry A European J

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“…100 Chiral BODIPYs have recently been studied more intensively in this context, and several chiral BODIPYs 101 have been reported; BODIPYs with chiral auxiliaries on the BODIPY skeleton or the boron atom, [102][103][104][105][106][107][108][109][110][111] axially chiral BODIPYs, [112][113][114][115] and BODIPYs containing an asymmetric boron. 116,117 However, BODIPYs with a molecular chirality and a chiral dipyrrin skeleton are still limited, and the seminal contributions by Nabeshima and coworkers are demonstrated in this section.…”

Section: Chiral N 2 and N 2 O X Dipyrrin Complexesmentioning

confidence: 97%

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

Chiba¹,

Nakamura²,

Matsuoka³

et al. 2020

Synlett

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The dipyrrin–metal complexes and especially the boron complex 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) have recently attracted considerable attention because of their interesting properties and possible applications. We have developed two unique and useful ways to extend versatility and usefulness of the dipyrrin complexes. The first one is the linear and macrocyclic oligomerization of the BODIPY units. These arrangements of the B–F moieties of the oligomerized BODIPY units provide sophisticated functions, such as unique recognition ability toward cationic guest, associated with changes in the photophysical properties by utilizing unprecedented interactions between the B–F and a cationic species. The second one is introduction of additional ligating moieties into the dipyrrin skeleton. The multidentate N2Ox dipyrrin ligands thus obtained form a variety of complexes with 13 and 14 group elements, which are difficult to synthesize using the original N2 dipyrrin derivatives. Interestingly, these unique complexes exhibit novel structures, properties, and functions such as guest recognition, stimuli-responsive structural conversion, switching of the optical properties, excellent stability of the neutral radicals, etc. We believe that these multifunctional dipyrrin complexes will advance the basic chemistry of the dipyrrin complexes and develop their applications in the materials and medicinal chemistry fields.1 Introduction2 Linear Oligomers of Boron–Dipyrrin Complexes3 Cyclic Oligomers of Boron–Dipyrrin Complexes4 A Cyclic Oligomer of Zinc–Dipyrrin Complexes5 Group 13 Element Complexes of N2Ox Dipyrrins6 Chiral N2 and N2Ox Dipyrrin Complexes7 Group 14 Element Complexes of N2O2 Dipyrrins8 Other N2O2 Dipyrrin Complexes with Unique Properties and Functions9 Conclusion

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“…Alternately, treatment of meso-aryl dipyrromethane 1 with one equivalent of appropriate NXS at -78°C in THF followed by oxidation with DDQ and complexation with BF 3 ⋅ OEt 2 in the presence of Et 3 N ( Figure 11A Figure 11B). 73 The amine group was introduced on the BODIPY core in a few steps. In the first step, the trialkyl substituted pyrrole was treated with sodium aqueous nitrite and acetic acid/acetic anhydride ( Figure 11C) to afford 3-amine substituted dipyrromethene 64.…”

Section: -Functionalized Bodipysmentioning

confidence: 99%