Palladium-Catalyzed Dehydrogenative Coupling of Furans with Styrenes

Aouf, Chahinez; Thiery, Emilie; Bras, Jean Le; Мuzart, Jacques

doi:10.1021/ol901570p

Cited by 71 publications

(42 citation statements)

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“…Compound 1 and 2 a, b were synthesized as procedures reported. [16] Absorption spectra were recorded on a PerkinElmer Lambda 35 UV/Vis Spectrometer. Photoluminescent (PL) spectra were carried out on a PerkinElmer LS55 Luminescence Spectrometer.…”

Section: Methodsmentioning

confidence: 99%

“…However, we propose that cocrystallized D-A systems have potential of the fluorescence recovery once force-induced phase separation occurs, which means that acceptors move away from adjacent fluorescent donors. 2,5-di(E)-distyrylfuran [16] 1 as an electron donor exhibited intensive greenish blue fluorescence both in solution and in crystal state, and planar p-conjugated structure leads to strong tendency to aggregate by p-p stacking. Meanwhile, we chose N-alkyl substituted maleimides as acceptors to quench fluorescence of donor via photo-induced electron transfer process (PET).…”

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confidence: 99%

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A Piezochromic Luminescent Complex: Mechanical Force Induced Patterning with a High Contrast Ratio

Luo

Song

et al. 2011

Chemistry A European J

101

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Piezochromic (mechanochromic) luminescent (PIEL) materials change their emission colors (bands) by applying appropriate pressure or other mechanical forces.[1] Their mechanical responsiveness provides fundamental basis for luminescence switches, information display/storage, and extremely significant pressure sensors in various fields. [2][3][4] The tuning of the luminescence of organic solids by mechanical forces has been realized through changing the chemical structures containing opened/closed cyclic forms [5] and double-bond E/Z configurations.[6] However, relatively high pressure is necessary to promote chemical reactions, [7] and poor reversibility has been considered as a drawback in such systems. In contrast, controlling the mode of molecular packing (aggregation states) is more attractive for both fundamental research and practical applications due to low pressure demand and good reversibility, but successful systems are quite limited. [8][9][10][11][12][13][14][15] A few reports mainly focused on transforming p-p aggregation modes of single conjugated materials under pressure, for example, (liquid) crystal to (liquid) crystal [8][9][10][11][12][13] or crystal to amorphous solid. [14][15] However, it is still difficult to predict and design materials with polymorphism. Herein, we utilize a binary complex to overcome the drawbacks from a single component system, and this strategy expands the range of PIEL materials to a large extent. In our approach, a fluorescent donor (D) and a nonemissive acceptor (A) are blent to form a binary complex to achieve piezochromic luminescence, in which the luminescence changes from quenching (black) to emitting (color) state once mechanical force is applied. We further confirmed the mechanism and realized mechanical force induced patterning. This strategy provides a new way to achieve piezochromic luminescence and special polymorphic materials are not necessary. In addition, unlike the transformation between two emission colors in traditional piezochromic luminescent materials, the contrast ratio is very high to favor observation by naked-eye due to very low fluorescence intensity in the quenching state.Many donor-acceptor systems reported have only fluorescence quenching process and no force-induced fluorescence recovery of donor. However, we propose that cocrystallized D-A systems have potential of the fluorescence recovery once force-induced phase separation occurs, which means that acceptors move away from adjacent fluorescent donors. 2,5-di(E)-distyrylfuran [16] 1 as an electron donor exhibited intensive greenish blue fluorescence both in solution and in crystal state, and planar p-conjugated structure leads to strong tendency to aggregate by p-p stacking. Meanwhile, we chose N-alkyl substituted maleimides as acceptors to quench fluorescence of donor via photo-induced electron transfer process (PET). [17][18] In fact, once the complex (1:1) of 1 and 2 a is deposited on the substrate, the fluorescence intensity of donor will be dramatically quenched. However, the fluore...

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

A Piezochromic Luminescent Complex: Mechanical Force Induced Patterning with a High Contrast Ratio

Luo

Song

et al. 2011

Chemistry A European J

101

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“…We noticed an induction period during our previous study that depends on the nature of the furan, the transformation being faster with electron-rich furans. [3] We also observed that the solvent can have a decisive influence on the course of the reaction. Low-coordinating solvents led to Heck-type products, [3] whereas coordinating solvents gave difurylalkanes.…”

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confidence: 61%

“…We have recently reported an efficient method for the coupling of furans with styrenes, which allowed the use of chlorinated and fluorinated substrates. [3] However, brominated substrates were reluctant to react. These compounds would allow the synthesis of valuable products for further functionalization through other cross-coupling reactions.…”

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confidence: 99%

Dehydrogenative Heck Reaction of Furans and Thiophenes with Styrenes under Mild Conditions and Influence of the Oxidizing Agent on the Reaction Rate

Vasseur

Мuzart

Bras

2011

Chemistry A European J

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In this study, the kinetics of the acid catalyzed hydrolysis of microcrystalline cellulose (Avicel PH101) to levulinic (LA) and formic (FA) acids was investigated in a batch reactor over the following range of conditions: 160–200°C, hydrochloric acid concentrations of 0.309–0.927 M (11.3–33.8 g/l), cellulose concentrations of 49.8–149 mM (8.06–24.1 g/l), and residence times of 0–50 min. The maximum LA yield of around 60% of theoretical was achieved for an initial cellulose concentration of 99.6 mM, acid concentration 0.927 M, and 180–200°C. A mathematical model and its analytical solution were developed to predict conversion of cellulose to LA and FA through glucose and hydroxymethyl‐2‐furfural based on an irreversible pseudo‐first order reaction. Rate analysis of each reaction indicated that the rate‐controlling step shifted from LA formation initially to HMF formation later. © 2011 American Institute of Chemical Engineers AIChE J, 2012

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“…Oxidative coupling of 2-methylfuran with activated alkenes in the presence of a stoichiometric amount of palladium compounds was reported in [6]. In addition, there are published data on catalytic alkenylation of furans in the presence of catalytic systems containing palladium complexes and copper(II) salts [7], in particular palladium acetate-tert-butyl hydroperoxide-benzoquinone [8], palladium acetate-molybdovanadophosphoric acid [9], and palladium acetate-copper acetate-benzoquinone [10].…”

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Synthetic transformations of higher terpenoids: XXV. Cross coupling of phlomisoic acid methyl ester with alkenes in the presence of oxidants

et al. 2011

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The reaction of phlomisoic acid methyl ester with styrene, catalyzed by Pd(OAc) 2 , in the presence of Cu(OAc) 2 and 1,4-benzoquinone in a mixture of propionic acid with diethyl ether gave the corresponding 15,16-distyryl derivative and only traces of 15-and 16-monosubstituted furanolabdanoids. Oxidative coupling of the title compound with methyl acrylate under analogous conditions afforded a mixture of 15-mono-, 16-mono-, and 15,16-dialkenylation products whose ratio changed during the process. The reaction was stereoselective, and the exocyclic double bond in the products had exclusively E configuration. * For communication XXIV, see [1]. Plant labdanoids are natural compounds possessing versatile pharmacological activity [2]. We previously described the synthesis of phlomisoic acid (I) [3] and its methyl ester II [4] from lambertianic acid which is an accessible metabolite of Siberian pine (Pinus sibirica). With a view to obtain diterpenoid derivatives with alkenyl substituents in the furan ring we examined oxidative coupling (Heck oxidative reaction) [5] of phlomisoic acid methyl ester (II) with alkenes. Oxidative coupling of 2-methylfuran with activated alkenes in the presence of a stoichiometric amount of palladium compounds was reported in [6]. In addition, there are published data on catalytic alkenylation of furans in the presence of catalytic systems containing palladium complexes and copper(II) salts [7], in particular palladium acetate-tert-butyl hydroperoxide-benzoquinone [8], palladium acetate-molybdovanadophosphoric acid [9], and palladium acetate-copper acetate-benzoquinone [10].The reaction of phlomisoic acid methyl ester (II) with styrene (2 equiv), catalyzed by Pd(OAc) 2 (0.1 equiv), in the presence of Cu(OAc) 2 (0.5 equiv) and 1,4-benzoquinone (0.1 equiv) in a 1 : 1 mixture of propionic acid with diethyl ether (35°C, 10 h) in an oxygen atmosphere resulted in the formation of (E)-15,16-distyryl-15,16-epoxylabdatrienoate III in 63% yield, the conversion being 90%. Increase of the reaction time until complete conversion of the initial compound did not improved the yield of III. When the reaction was performed using an equimolar amount of styrene, other conditions being equal, the product was 15,16-distyryl derivative III as well (yield 32%, conversion 40%). In the presence of 0.05 equiv of Pd(OAc) 2 the yield of III was 23% (conversion 57%). In these cases, only trace amounts of monosubstituted furanolabdanoids IV and V were detected. Interestingly, the reaction of II with 1 equiv of styrene in dioxane-propionic acid (5 : 1) in the presence of a stoichiometric amount of palladium acetate at 100°C (10 h) also afforded (E)-15,16-distyryllabdatrienoate III as the only product (yield 19%, conversion 57%) and was accompanied by considerable tarring.In the reaction of phlomisoic acid methyl ester (II) with methyl acrylate, the complete conversion was attained in 80 h. The products were 15,16-bis(3-methoxy-3-oxoprop-1-en-1-yl)-, 16-(3-methoxy-3-oxoprop-1-en-1-yl)-, and 15-(3-methoxy-3-oxoprop-1-en-

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Palladium-Catalyzed Dehydrogenative Coupling of Furans with Styrenes

Abstract: Under palladium(II)-catalyzed and oxidative conditions, the coupling of furans with styrenes leads to the formation of Heck-type products in medium to good yields. The reaction is highly regio- and stereoselective, giving trans-olefins predominantly.

Cited by 71 publications

References 34 publications

A Piezochromic Luminescent Complex: Mechanical Force Induced Patterning with a High Contrast Ratio

A Piezochromic Luminescent Complex: Mechanical Force Induced Patterning with a High Contrast Ratio

Dehydrogenative Heck Reaction of Furans and Thiophenes with Styrenes under Mild Conditions and Influence of the Oxidizing Agent on the Reaction Rate

Synthetic transformations of higher terpenoids: XXV. Cross coupling of phlomisoic acid methyl ester with alkenes in the presence of oxidants

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