Mild Pd/Cu-Catalyzed Sila-Sonogashira Coupling of (Hetero)aryl Bromides with (Hetero)arylethynylsilanes under PTC Conditions

Bellina, Fabio; Lessi, Marco

doi:10.1055/s-0031-1290601

Cited by 28 publications

(15 citation statements)

References 5 publications

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“…In details, when ((4-ethynylphenyl)ethynyl)trimethylsilane (3) [15] was reacted with bromides 4a-b in the presence of 5 mol% PdCl 2 (PhCN) 2 , 10 mol% t-Bu 3 P, 2.0 equiv DABCO as the base in MeCN at room temperature, [16] the required alkynes 5a-b were isolated in 60 and 65% yield, respectively (Scheme 1). The target chromophores 1b-d were successfully obtained from the Sila-Sonogashira type coupling under PTC conditions, according to a recent synthetic protocol developed by us, [17] involving trimethylsilylalkynes 5a-b and thienyl bromides 4b-d. In this way, thiophene-based derivatives 1b-d were isolated in 50-95 % yields.…”

Section: Resultsmentioning

confidence: 99%

Computational Design, Synthesis, and Mechanochromic Properties of New Thiophene‐Based π‐Conjugated Chromophores

Prampolini

Bellina

Biczysko

et al. 2012

Chemistry A European J

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The possibility of exploiting supramolecular architectures for the preparation of innovative mechanochromic devices has been extended by designing novel thienyl-substituted 1,4-bis(ethynyl)benzene dyes, which are characterized by a conjugated, rigid, rodlike core structure. This new family of chromophores was synthesized according to a simple two-step sequential cross-coupling reaction, and the optical properties were investigated in solution and in a polymeric matrix. To tune the mechanochromic performances in smart polymer materials, a virtual screening was set up that was able to select a derivative with optimal spectral features. The effective combination of experimental and computational investigations allowed us to spot those homologues with already potential anisotropic and aggregachromic features and characterized by the best spectral properties and luminescent response. The best candidate was synthesized and dispersed into a polyethylene matrix, indeed achieving an "in silico designed" mechanochromic material. Besides the specific applications of this novel material, the integration of computational and experimental techniques reported here defines an efficient protocol that can be applied to make a selection among similar dye candidates, which constitute the essential responsive part of such supramolecular devices.

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Section: Resultsmentioning

confidence: 99%

Computational Design, Synthesis, and Mechanochromic Properties of New Thiophene‐Based π‐Conjugated Chromophores

Prampolini

Bellina

Biczysko

et al. 2012

Chemistry A European J

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“…According to our previously published procedure, [32] to a mixture of 6,6'bis((trimethylsilyl)ethynyl)-2,2'-bipyridine (2) N, 7.0.…”

Section: 6'-bis((5-methylthiophen-2-yl)ethynyl)-22'-bipyridine (1a)mentioning

confidence: 99%

“…According to our previously published procedure, [32] were determined by the Benesi-Hildebrand method. [33] Fluorescence spectra of solutions were recorded at room temperature with the help of a Horiba Jobin-Yvon Fluorolog ® -3 spectrofluorometer.…”

Section: 6'-bis((5-methoxythiophen-2-yl)ethynyl)-22'-bipyridine (1b)mentioning

confidence: 99%

Zn(II)-bisthienylethynylbipyridine complex: Preparation, characterization and vapochromic behaviour in polymer films

et al. 2014

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In the present work, we report the vapochromic behaviour of PMMA films doped with small amounts of 1a:Zn fluorophore, a Zn 2+ adduct of the bisthienylethynylbipyridine ligand. 1a:Zn exhibited polarity-dependent changes in the fluorescence spectral properties when dissolved in solvents with different polarity index, indicating that its fluorescence states are of intramolecular charge transfer character. When 1a:Zn was dispersed in the PMMA matrix, its emission resulted barely influenced by the polymer environment. By contrast, 1a:Zn/PMMA films showed a significant variation of its emission with a 40 nm red-shift when exposed to a saturated atmosphere of dichloromethane. This vapochromic behaviour was much less evident when progressive amounts of methanol were added to dichloromethane due to both lower vapour pressure and limited interaction of the former with PMMA. The experiments revealed also that the rate constants associated with the vapochromic behaviour were affected by solvent composition and easily determined by luminescent experiments.

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“…The palladium catalyzed carbon-carbon bond forming reactions are of great importance in modern synthetic organic chemistry [1]. Among well-known carbon-carbon coupling reactions, the Sonogashira-Hagihara cross-coupling stands out as a unique method enabling the coupling between (sp) carbon and (sp 2 ) carbon atoms [2][3][4][5][6][7][8][9]. The reaction products containing such bonds have found applications in a wide range of synthetic reactions such as biologically active compounds and pharmaceuticals [10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Palladium supported on bis(indolyl)methane functionalized magnetite nanoparticles as an efficient catalyst for copper-free Sonogashira-Hagihara reaction

Gholinejad

Neshat

Zareh

et al. 2016

Applied Catalysis A: General

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A novel heterogeneous catalyst based on palladium nanoparticles supported on 3,3'-bisindolyl(4hydroxyphenyl)methane functionalized magnetite (Fe3O4) nanoparticles was synthesized, characterized and used as catalyst for Sonogashira-Hagihara reaction. The alkynylation of a variety of aryl iodides and aryl bromides with terminal alkynes was carried out at 60 °C under copper and phosphane-free conditions using N,N-dimethyl acetamide as solvent, DABCO as base and low Pd loadings (0.18 mol%) under air. In the case of aryl chlorides, the reaction was carried out at 120 ºC in the presence of tetra-n-butylammonium bromide (TBAB) and 0.36 mol% of Pd catalyst. The heterogeneous palladium catalyst introduced in this study is recoverable by an external magnet and it can be used for seven consecutive runs without a significant loss in catalytic activity.

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Mild Pd/Cu-Catalyzed Sila-Sonogashira Coupling of (Hetero)aryl Bromides with (Hetero)arylethynylsilanes under PTC Conditions

Cited by 28 publications

References 5 publications

Computational Design, Synthesis, and Mechanochromic Properties of New Thiophene‐Based π‐Conjugated Chromophores

Computational Design, Synthesis, and Mechanochromic Properties of New Thiophene‐Based π‐Conjugated Chromophores

Zn(II)-bisthienylethynylbipyridine complex: Preparation, characterization and vapochromic behaviour in polymer films

Palladium supported on bis(indolyl)methane functionalized magnetite nanoparticles as an efficient catalyst for copper-free Sonogashira-Hagihara reaction

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