8-Alkenylborondipyrromethene dyes. General synthesis, optical properties, and preliminary study of their reactivity

Arroyo, Ismael J.; Hu, Rongrong; Tang, Ben Zhong; López, Fabiola I.; Peña‐Cabrera, Eduardo

doi:10.1016/j.tet.2011.07.067

Cited by 54 publications

(37 citation statements)

References 18 publications

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“…In this way, there is no electronic coupling between the enol group and the BODIPY core, and the deleterious effect of the double bond placed at the meso position on the fluorescence efficiency of BODIPY is avoided. [14,31] Theoretical calculations predict that the acac group is in its enolic form, in agreement with NMR spectroscopy and X-ray results (Figures 2 and 3 and Figure S1 in the Supporting Information). Scheme 2.…”

Section: Photophysical Propertiessupporting

confidence: 72%

Straightforward Synthetic Protocol for the Introduction of Stabilized C Nucleophiles in the BODIPY Core for Advanced Sensing and Photonic Applications

Gutiérrez-Ramos

Bañuelos

Arbeloa

et al. 2014

Chemistry A European J

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A straightforward synthetic protocol to directly incorporate stabilized 1,3‐dicarbonyl C nucleophiles to the meso position of BODIPY (4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene) is reported. Soft nucleophiles generated by deprotonation of 1,3‐dicarbonyl derivatives smoothly displace the 8‐methylthio group from 8‐(methylthio)BODIPY analogues in the presence of CuI thiophenecarboxylate in stoichiometric amounts at room temperature. Seven highly fluorescent new derivatives are prepared with varying yields (20–92 %) in short reaction times (5–30 min). The excellent photophysical properties of the new dyes allow focusing on applications never analyzed before for BODIPYs substituted with stabilized C nucleophiles such as pH sensors and lasers in liquid and solid state, highlighting the relevance of the synthetic protocol described in the present work. The attainment of these dyes, with strong UV absorption and highly efficient and stable laser emission in the green spectral region, concerns to one of the greatest challenges in the ongoing development of advanced photonic materials with relevant applications. In fact, organic dyes with emission in the green are the only ones that allow, by frequency‐doubling processes, the generation of tunable ultraviolet (250‐350 nm) radiation, with ultra‐short pulses.

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Section: Photophysical Propertiessupporting

confidence: 72%

Straightforward Synthetic Protocol for the Introduction of Stabilized C Nucleophiles in the BODIPY Core for Advanced Sensing and Photonic Applications

Gutiérrez-Ramos

Bañuelos

Arbeloa

et al. 2014

Chemistry A European J

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“…Peña‐Cabrera and co‐workers developed a new strategy for the synthesis of BODIPY derivatives through a Liebeskind–Srogl cross‐coupling reaction (Scheme ) . Under their modified reaction conditions, a variety of aryl,, and alkenyl boronic acids smoothly underwent the cross‐coupling reaction with 8‐thiomethylBODIPY ( 150 a ) or disubstituted 8‐thiomethylBODIPY ( 150 b ), thereby delivering the target BODIPY derivatives in high yields. Aside from boronic acids, arylstannanes were also good coupling partners in this procedure .…”

Section: Applicationsmentioning

confidence: 99%

“…Under their modified reaction conditions, a variety of aryl,, and alkenyl boronic acids smoothly underwent the cross‐coupling reaction with 8‐thiomethylBODIPY ( 150 a ) or disubstituted 8‐thiomethylBODIPY ( 150 b ), thereby delivering the target BODIPY derivatives in high yields. Aside from boronic acids, arylstannanes were also good coupling partners in this procedure . With azido boronic acids, substrate 150 a could be converted into triazoles in one pot .…”

Section: Applicationsmentioning

confidence: 99%

The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

et al. 2018

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The Pd-catalyzed, Cu I Àcarboxylate-mediated crosscoupling reactiono fo rganosulfur compounds with nucleophilic organometallic reagents is knowna st he Liebeskind-Srogl cross-coupling reaction. Owing to the readily available starting materials and neutral reactionc onditions, it has become an attractive procedure for the formation of carbonÀcarbon bonds, in particularf or cases in whicht radi-tional methods had failed. Since the seminal work of Liebeskind and Srogl in 2000, this reactionh as received intense attentionf rom the synthetic community.I nt his Focus Review,w eh ighlight recent advances in this intriguing cross-coupling reactiona nd its applications in organic synthesis.Scheme1.Liebeskind-Srogl cross-coupling reaction.Scheme2.The original Liebeskind-Sroglc ross-coupling reaction.d ba = dibenzylideneacetone, TFP = tri-2-furanylphosphine [a] Dr.Scheme4.Cross-coupling reaction between a-amino acid thiol esters and organostannanes. Cbz = benzyloxycarbonyl.Scheme5.Cross-coupling reaction between thiol esters and B-alkyl-9-BBN. 9-BBN = 9-borabicyclo[3.3.1]nonane.Scheme6.One-pothydroboration/intramolecular-cross-couplingr eaction between thiol esters and B-alkyl-9-BBN. DIPEA = N,N-diisopropylethylamine.Scheme7.Cross-coupling reaction between thiol esters andorganoindium reagents.Scheme8.Cross-coupling reaction between thiol esters andorganosilicon reagents. TBAF = tetra-n-butylammonium fluoride.Scheme9.Intramolecular cross-coupling reaction between thiol esters and olefins.Scheme38. Cross-coupling reaction between diaryld isulfides and boronicacids/terminal-alkynes.Scheme55. Synthesis of the C 15 ÀC 36 segment of goniodomin A. TBS = tert-butyldimethylsilyl, TBDPS = tert-butyldiphenylsilyl.Scheme56. To talsynthesis of verbenachalcone. MOM = methoxymethyl.Scheme57. Synthesis of enigmol and its stereoisomers. Boc = tert-butyloxycarbonyl.Scheme58. To talsynthesis of (À)-agelastatins A-F.Scheme59. Synthesis of quinone-containing salvinorin Aa nalogues.Scheme60. Synthesis of Soai-type aldehydes.

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“…[17] On the other hand, BODIPY platform b bearing 3,5-chloro groups undergoes milder Pd 0 -catalyzed cross-coupling reactions and nucleophilic substitution reactions at these positions, producing a variety of functionalized BODIPYs for various applications. [18] Functionalizations at the 8-position of BODIPYs are reported for platform c , [15, 19] which undergoes nucleophilic addition/elimination and Liebeskind–Srogl cross-coupling reactions, and also for platform d bearing an 8-chloro group. [16] Compared with the 8-methylthio-BODIPY c , platform d is more versatile, reacting with a variety of N-, O-, and S-centered nucleophiles, as well as under a variety of Pd 0 -catalyzed Stille, Suzuki, and Sonogashira coupling conditions, producing the corresponding functionalized BODIPYs in good to quantitative yields.…”

Section: Introductionmentioning

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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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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8-Alkenylborondipyrromethene dyes. General synthesis, optical properties, and preliminary study of their reactivity

Cited by 54 publications

References 18 publications

Straightforward Synthetic Protocol for the Introduction of Stabilized C Nucleophiles in the BODIPY Core for Advanced Sensing and Photonic Applications

Straightforward Synthetic Protocol for the Introduction of Stabilized C Nucleophiles in the BODIPY Core for Advanced Sensing and Photonic Applications

The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

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

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