Selective Green Coupling of Alkynyltins and Allylic Halides to Trienynes <i>via</i> a Tandem Double Stille Reaction

Meana, Isabel; Albéniz, Ana C.; Espinet, Pablo

doi:10.1002/adsc.201000430

Cited by 29 publications

(16 citation statements)

References 24 publications

(8 reference statements)

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“…We chose to utilize Stille coupling instead of Sonogashira coupling because we had previously found that this method gives higher yields for installing phenylethynyl pyrrolic substituents [9]. The fluorinated tributyltinphenylacetylene analogs for the synthesis of L3 and L4 were synthesized according to literature procedures and used without purification [35–36]. The Stille cross coupling reactions for the synthesis of L3 and L4 were monitored by MALDI–TOF–MS and were found to not be complete after increasing the reaction time to 48 h, so the reaction time was increased to 96 h with the addition of more catalyst and tributyltin reactant after 48 h. These modifications were deemed necessary to push the reaction towards completion and aid in purification of the free ligand.…”

Section: Resultsmentioning

confidence: 99%

“…ADP, ADPI 2 , WS3, BF 2 (WS3), and Zn(WS3) 2 were synthesized and purified according to literature procedures with minor modifications [2,5,9,33–34]. (4-Fluorophenylethynyl)tributyltin (for the synthesis of L3), and [4-(trifluoromethyl)phenyl](tributyltin)acetylene (for the synthesis of L4) were synthesized according to literature procedures with minor modifications and used without purification [35–36]. …”

Section: Methodsmentioning

confidence: 99%

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Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

Etheridge¹,

Fernando²,

Pejić³

et al. 2016

Beilstein J. Org. Chem.

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SummaryHomoleptic zinc(II) complexes of di(phenylacetylene)azadipyrromethene (e.g., Zn(WS3)2) are potential non-fullerene electron acceptors for organic photovoltaics. To tune their properties, fluorination of Zn(WS3)2 at various positions was investigated. Three fluorinated azadipyrromethene-based ligands were synthesized with fluorine at the para-position of the proximal and distal phenyl groups, and at the pyrrolic phenylacetylene moieties. Additionally, a CF3 moiety was added to the pyrrolic phenyl positions to study the effects of a stronger electron withdrawing unit at that position. The four ligands were chelated with zinc(II) and BF2 + and the optical and electrochemical properties were studied. Fluorination had little effect on the optical properties of both the zinc(II) and BF2 + complexes, with λmax in solution around 755 nm and 785 nm, and high molar absorptivities of 100 × 103 M−1cm−1 and 50 × 103 M−1cm−1, respectively. Fluorination of Zn(WS3)2 raised the oxidation potentials by 0.04 V to 0.10 V, and the reduction potentials by 0.01 V to 0.10 V, depending on the position and type of substitution. The largest change was observed for fluorine substitution at the proximal phenyl groups and CF3 substitution at the pyrrolic phenylacetylene moieties. The later complexes are expected to be stronger electron acceptors than Zn(WS3)2, and may enable charge transfer from other conjugated polymer donors that have lower energy levels than poly(3-hexylthiophene) (P3HT).

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

Etheridge¹,

Fernando²,

Pejić³

et al. 2016

Beilstein J. Org. Chem.

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“…NMR spectra were recorded at rt with Bruker AM 250, DPX 250, Avance II 300, Avance 400 and Avance III HD 500 spectrometers. Chemical shifts are referenced to (residual) solvent signals ( 1 H/ 13 46 4-(trimethylsilyl)pyrazole, 47 and 3,5-di(tert-butyl)pyrazole 48 are literature known; the amount of OEt 2 present in the samples of Li 2 [1,1′-fc(BH 3 ) 2 ]·(OEt 2 ) 0.25 after prolonged storage in a screwcapped vial in the glove-box was determined by 1 H NMR spectroscopy.…”

Section: Experimental Methodsmentioning

confidence: 99%

Synthesis and characterisation of the complete series of B–N analogues of triptycene

et al. 2014

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The reaction between the bisborate Li2[o-C6H4(BH3)2] and 2 equivalents of an appropriate pyrazole derivative (Hpz(R)) in the presence of Me3SiCl yields o-phenylene-bridged pyrazaboles HB(μ-pz(R))2(μ-o-C6H4)BH (3a-3e; Hpz(R) = 4-iodopyrazole (3a), 4-(trimethylsilyl)pyrazole (3b), 3,5-dimethylpyrazole (3c), 3,5-di(tert-butyl)pyrazole (3d), 3,5-bis(trifluoromethyl)pyrazole (3e)). The synthesis approach thus provides access to uncharged B-N triptycenes bearing (i) functionalisable groups, (ii) electron-donating or -withdrawing substituents and (iii) pyrazole rings of varying steric demand. Treatment of p-R*C6H4BBr2 with the potassium tris(pyrazol-1-yl)borates K[HBpz3] or K[p-R*C6H4Bpz3] yields cationic pyrazolyl-bridged pyrazaboles [p-BrC6H4B(μ-pz)3BH]Br ([4a]Br) and [p-R*C6H4B(μ-pz)3Bp-C6H4R*]Br (R* = Br ([4b]Br), I ([4c]Br), SiMe3 ([4d]Br)), which can be regarded as full B-N analogues of triptycene. The B-H bonds of 3b and [4a]Br are unreactive towards tBuC[triple bond, length as m-dash]CH even at temperatures of 80 °C, thereby indicating an appreciable thermal stability of the corresponding B-N cage bonds. Most of the cage compounds are sufficiently inert towards water to allow quick aqueous workup. However, NMR spectroscopy in CD3OD solution reveals degradation of 3b or [4a]Br to the corresponding pyrazoles and o-C6H4(B(OCD3)2)2 or p-BrC6H4B(OCD3)2/B(OCD3)3. The diphenylated species [4b]Br is significantly more stable under the same measurement conditions; even after 76 d, most of the material degrades only to the stage of the syn/anti-pyrazaboles p-BrC6H4(CD3O)B(μ-pz)2B(OCD3)p-C6H4Br (11a/11b). A derivatisation of [4c]Br with nBu3SnC≡CtBu through Stille-type coupling reactions furnishes the alkynyl derivative [p-tBuC≡CC6H4B(μ-pz)3Bp-C6H4C≡CtBu]Br ([4e]Br). Larger B-N aggregates are also accessible: treatment of the tetrakisborate Li4[1,2,4,5-C6H2(BH3)4] with 4 equivalents of Hpz(R) in the presence of Me3SiCl leads to the corresponding B-N pentiptycenes (Hpz(R) = 3,5-bis(trifluoromethyl)pyrazole (14a), 4-(trimethylsilyl)pyrazole (14b), 3,5-dimethylpyrazole (14c), 3,5-di(tert-butyl)pyrazole (14d)).

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“…Norbornenes are extremely convenient monomers for the targeted design of polymer materials with desired properties owing to their availability and the capability to polymerize via different ways. Polymers from substituted norbornenes could possess various valuable properties depending on the substituent nature, such as high glass transition temperatures, optical transparency, high gas permeability, low moisture absorption, the inertness of main chains, and so on. Usually norbornenes obtaining by Diels‐Alder reaction are mixtures of exo‐ and endo‐ isomers .…”

Section: Introductionmentioning

confidence: 99%

Stereoselective synthesis and polymerization of Exo‐5‐trimethylsilylnorbornene

Alentiev

Bermeshev

Старанникова

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Herein the stereoselective two‐step synthesis of pure exo‐5‐trimethylsilylnorbornene is reported. The monomer proved to be highly reactive in both metathesis and addition polymerization. ROMP polymerization was catalyzed by the first‐generation Grubbs catalyst. High‐molecular‐weight saturated addition polymers were prepared using nickel or palladium complexes as precatalysts and Na+[B(3,5‐(CF3)2C6H3)4]− and/or MAO as cocatalysts. The obtained addition polynorbornenes are highly gas permeable and microporous materials possessing large free volume and BET surface area (up to 540 m2/g). The influence of the substituent orientation (exo‐ vs. exo‐/endo‐mixture) on polymer properties was established. The metathesis polymer based on exo‐isomer exhibits 1.5‐ to 2‐fold increase of permeability coefficients for all gases in comparison to the similar polymer based on the mixture of exo‐ and endo‐isomers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1234–1248

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Selective Green Coupling of Alkynyltins and Allylic Halides to Trienynes via a Tandem Double Stille Reaction

Cited by 29 publications

References 24 publications

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

Synthesis and characterisation of the complete series of B–N analogues of triptycene

Stereoselective synthesis and polymerization of Exo‐5‐trimethylsilylnorbornene

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