- Palladium-catalyzed highly selective ortho-halogenation (I, Br, Cl) of arylnitriles via sp2 C-H bond activation using cyano as directing group
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A palladium-catalyzed ortho-halogenation (I, Br, Cl) of arylnitrile is described. The optimal reaction conditions were identified after examining various factors such as catalyst, additive, solvent, and reaction temperature. Using cyano as the directing group, the halogenation reaction gave good to excellent yields. The method is compatible to the arylnitriles with either electron-withdrawing or electron-donating groups. The reaction is available to the substrate in at least gram scale. The present method was successfully applied to the synthesis of the precursors of paucifloral F and isopaucifloral F.
- Du, Bingnan,Jiang, Xiaoqing,Sun, Peipei
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p. 2786 - 2791
(2013/04/24)
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- Synthesis and properties of anthrylene-substituted phenyleneethynylene dyes having amino/cyano group(s) and their application to dye-sensitized solar cells
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A series of anthrylene-substituted phenyleneethynylene dyes having amino/cyano group(s) were prepared by repeating Sonogashira coupling between aryl halides and terminal acetylenes. In UVvis absorption spectra, the 9,10-anthrylene-substituted dyes showed a strong absorption band of which λmax was located from 502 to 521 nm and ε was more than 5.2 × 104L mol-1 cm-1 indicating a highly expanded π-system in comparison with 1,5-anthrylene dye (λmax = 431 nm, ε= 2.6 × 104L mol-1 cm-1). LippertMataga plots demonstrated that the amino- and cyano-substituted dyes underwent larger charge separation in the excited states. These acetylenic dyes served as sensitizers of dye-sensitized solar cell to achieve 5.0% of photo-to-current energy conversion efficiency.
- Yang, Xin,Kajiyama, Shingo,Fang, Jing-Kun,Xu, Feng,Uemura, Yu,Koumura, Nagatoshi,Hara, Kohjiro,Orita, Akihiro,Otera, Junzo
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supporting information; experimental part
p. 687 - 697
(2012/07/30)
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- A safe and reliable procedure for the iododeamination of aromatic and heteroaromatic amines in a continuous flow reactor
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A method for the safe and reliable iododeamination of aromatic and heteroaromatic amines under copper-free conditions is described and its scope is evaluated.
- Malet-Sanz, Laia,Madrzak, Julia,Holvey, Rhian S.,Underwood, Toby
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experimental part
p. 7263 - 7267
(2010/03/03)
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- Block modification of rod-shaped π conjugated carbon frameworks with donor and acceptor groups toward highly fluorescent molecules: Synthesis and emission characteristics
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To create organic molecules that are highly fluorescent at a longer wavelength region, we investigated the synthesis (using Pd-catalyzed cross-coupling) and photophysical properties (Φ f, λ em, τ , λ abs, and ε ) of the following π conjugated molecular rods consisting of p-phenyleneethynylene units modified by donor (OMe) and/or acceptor (CN) groups: (1) side-donor modification systems (SD systems), (2) side-acceptor modification systems (SA systems), and (3) systems consisting of a donor block and an acceptor block (BL systems). As a consequence, very high Φ f values (>0.95) were obtained for BL systems. Bathochromic shifts of λ em for the same π conjugation length were largest for BL systems. Thus we succeeded in creating highly efficient light emitters at a longer wavelength region by block modification (e.g., Φ f = 0.97, λ em = 464 nm for BL-9). Considerably intense solid emission (Φ f ～ 0.5) at a longer wavelength region (500- 560 nm) was also found for BL systems. It has been found that BL-6 and BL-8 exhibit interesting two photon absorption characteristics. This journal is The Royal Society of Chemistry.
- Ochi, Takanori,Yamaguchi, Yoshihiro,Wakamiya, Tateaki,Matsubara, Yoshio,Yoshida, Zen-Ichi
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supporting information; scheme or table
p. 1222 - 1231
(2008/10/09)
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- New fluorophores with rod-shaped polycyano π-conjugated structures: Synthesis and photophysical properties
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Novel rod-shaped polycyano-oligo(phenyleneethynylene)s were synthesized by Pd cross-coupling reaction. Polycyano groups were found to greatly improve the emission efficiency (Φf) of OPEs. By the end donor modification, we achieved the creation of very intense blue light-emitting fluorophore with the SMe group (Φf) = 0.972, log ε 4.89, λ em 455 nm) and very intense yellow light-emitting fluorophore with the NMe2 group (Φf = 0.999, log ε 4.75, λem 555 nm). Contrasting Φf solvent dependency of 6 and 7 and a linear relationship between Φf and σp-X over the whole region of σp-X were also found.
- Yamaguchi, Yoshihiro,Ochi, Takanori,Wakamiya, Tateaki,Matsubara, Yoshio,Yoshida, Zen-Ichi
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p. 717 - 720
(2007/10/03)
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- Aromatic allylation via diazotization: Variation of the allylic moiety and a short route to a benzazepine derivative
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A continued study of the recently discovered diazotizative allylation (DiazAll) reaction of aniline derivatives is reported. Several allyl reagents, commonly used in radical allylation reactions, were evaluated, and some of these reagents resulted in ally
- Ek, Fredrik,Wistrand, Lars-Goeran,Frejd, Torbjoern
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p. 1911 - 1918
(2007/10/03)
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- The Synthesis and Transition Temperatures of Some Lateral Cyano-Substituted-1,1':4',1''-terphenyls
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In recent years we have used palladium-catalysed cross-coupling procedures to prepare a large number of very interesting lateral mono- and di-fluoro-substituted terphenyls.Similar methodology has been applied in the synthesis of lateral cyano-substituted terphenyls to assess the extent to which the mesophases of such systems can tolerate the larger cyano group; the synthetic routes to these compounds are discussed in detail.The compounds with the lateral cyano-substituent in the centre ring have very low melting points and liquid crystal phases exhibited (SC, SA and nematic) are dependent on the terminal substituents.The compounds with the cyano-substituent at the edge of the terphenyl core are still quite low melting and they have very wide SA ranges. Keywords: lateral cyano-substitution, 1,1':4',1''-terphenyls, palladium-catalysed cross-coupling
- Hird, Michael,Gray, George W.,Toyne, Kenneth J.
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p. 205 - 221
(2007/10/02)
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