- Facile one-pot synthesis of diarylacetylenes from arylaldehydes: Via an addition-double elimination process
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A practical one-pot protocol has been developed to synthesize diarylacetylenes from arylaldehydes by treatment with 1-(arylmethyl)benzotriazoles and LiN(SiMe3)2. The reaction proceeded through imine formation, Mannich-type addition and double elimination to deliver products in up to 99% yields with broad substrate scope. In addition, gram-scale synthesis of 1-bromo-4-(phenylethynyl)benzene has been demonstrated.
- Chen, Jianyang,Zhang, Xuan,Wu, Jiajun,Wang, Rui,Lei, Chunlin,An, Yanan
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p. 4701 - 4705
(2021/06/11)
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- A new approach to large scale production of dimethyl sulfone: A promising and strong recyclable solvent for ligand-free Cu-catalyzed C-C cross-coupling reactions
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Dimethyl sulfone (DMSN) was easily prepared through efficient oxidation of dimethyl sulfoxide (DMSO) and used as a strong and green solvent for organic reactions. A mixture of HNO3/NaOCl was used as an oxidizing agent for efficient oxidation of DMSO to DMSN. The effect of DMSN was evaluated for copper-catalyzed coupling reactions. It is worth noting that DMSN could play the role of a ligand for copper ions. A general survey was accomplished for various types of C-C cross-coupling reactions catalyzed by CuI in DMSN in the absence of any ligand. Moderate to good yields were achieved for Sonogashira, Heck, and Suzuki cross-coupling reactions. Finally, DMSN was recovered and reused for several consecutive runs without any loss of its activity.
- Cheng, Shen,Wei, Wei,Zhang, Xingyu,Yu, Hewei,Huang, Mingming,Kazemnejadi, Milad
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p. 2069 - 2076
(2020/04/07)
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- Conjugated mesoporous polyazobenzene–Pd(II) composite: A potential catalyst for visible-light-induced Sonogashira coupling
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We herein report the direct harnessing of visible light energy by a novel semiconducting azobenzene-based colloidal porous organic polymer, B3-Azo4 amenable to post-synthetic Pd(II)-complexation for photo-induced Sonogashira coupling using polymer → metal energy transfer process. Completely mesoporous nano-sized particles of the obtained organic network manifested excellent Pd(II) coordinating ability and afforded desired catalytic products at room temperature under aerobic condition in aqueous medium. The protocol remained valid for different aromatic and aliphatic substrates as well. A possible reaction mechanism for photo-mediated Sonogashira coupling catalyzed by Pd-B3-Azo4 is also proposed.
- Nath, Ipsita,Chakraborty, Jeet,Khan, Anish,Arshad, Muhammad N.,Azum, Naved,Rab, Malik A.,Asiri, Abdullah M.,Alamry, Khalid A.,Verpoort, Francis
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p. 183 - 189
(2019/08/07)
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- The Direct Conversion of α-Hydroxyketones to Alkynes
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Alkynes are highly important functional groups in organic chemistry, both as part of target structures and as versatile synthetic intermediates. In this study, a protocol for the direct conversion of α-hydroxyketones to alkynes is reported. In combination with the variety of synthetic methods that generate the required starting materials by forming the central C-C bond, it enables a highly versatile fragment coupling approach toward alkynes. A broad scope for this novel transformation is shown alongside mechanistic insights. Furthermore, the utility of our protocol is demonstrated through its application in concert with varied α-hydroxyketone syntheses, giving access to a broad spectrum of alkynes.
- Ghiringhelli, Francesca,Nattmann, Lukas,Bognar, Sabine,Van Gemmeren, Manuel
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p. 983 - 993
(2019/01/24)
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- Supramolecular photocatalyst of Palladium (II) Encapsulated within Dendrimer on TiO2 nanoparticles for Photo-induced Suzuki-Miyaura and Sonogashira Cross-Coupling reactions
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In this study, synthesis, characterization and catalytic performance of a novel supramolecular photocatalytic system including palladium (II) encapsulated within amine-terminated poly (triazine-triamine) dendrimer modified TiO2 nanoparticles (Pd (II) [PTATAD] @ TiO2) is presented. The obtained nanodendritic catalyst was characterized by FT-IR, ICP-AES, XPS, EDS, TEM, TGA and UV-DRS. The as-prepared nanodendritic catalyst was shown to be highly active, selective, and recyclable for the Suzuki–Miyaura and Sonogashira cross-coupling of a wide range of aryl halides including electron-rich and electron-poor and even aryl chlorides, affording the corresponding biaryl compounds in good to excellent yields under visible light irradiation. This study shows that visible light irradiation can drive the cross-coupling reactions on the Pd (II) [PTATAD] @ TiO2 under mild reaction conditions (27–30?°C) and no additional additives such as cocatalysts or phosphine ligands. So, we propose that the improved photoactivity predominantly benefits from the synergistic effects of Pd (II) amine-terminated poly (triazine-triamine) dendrimer on TiO2 nanoparticles that cause efficient separation and photogenerated electron–hole pairs and photoredox capability of nanocatalyst which all of these advantages due to the tuning of band gap of catalyst in the visible light region.
- Eskandari, Ameneh,Jafarpour, Maasoumeh,Rezaeifard, Abdolreza,Salimi, Mehri
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- Radiosynthesis of SPECT tracers: Via a copper mediated 123I iodination of (hetero)aryl boron reagents
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A general method for the copper mediated nucleophilic 123I-iodination of (hetero)aryl boronic esters and acids has been developed. The broad substrate scope of this radiosynthetic approach allows access to [123I]DPA-713, [123I]IMPY, [123I]MIBG and [123I]IPEB that are four commonly used SPECT radiotracers. Our results infer that aryl boronic reagents can now be employed as common precursors for both fluorine-18 and iodine-123 radiolabelling.
- Wilson, Thomas C.,McSweeney, Greg,Preshlock, Sean,Verhoog, Stefan,Tredwell, Matthew,Cailly, Thomas,Gouverneur, Véronique
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supporting information
p. 13277 - 13280
(2016/11/17)
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- Boronate ester post-functionalization of PPEs: versatile building blocks for poly(2,2′-(1-(4-(1,2-di(thiophen-2-yl)vinyl)phenyl)-2-(2,5-dioctylphenyl)ethene-1,2-diyl)dithiophene) and application in field effect transistors
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A convenient and scalable strategy for post-functionalization of poly(phenylene-ethynylene)s and phenylene-ethynylene arrays from boronate ester derivatives using the thienyl group as an example. Furthermore, poly(2,2′-(1-(4-(1,2-di(thiophen-2-yl)vinyl)phenyl)-2-(2,5-dioctylphenyl)ethene-1,2-diyl)dithiophene) showed good field-effect transistor performance with an excellent mobility up to 0.723 cm2 V-1 s-1 and an on-off ratio of 104.
- Yang, Junwei,Chen, Moyun,Ma, Ji,Huang, Wei,Zhu, Haoyun,Huang, Yuli,Wang, Weizhi
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supporting information
p. 10074 - 10078
(2015/10/12)
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- Copper(i) catalyzed Sonogashira reactions promoted by monobenzyl nicotinium chloride, a N-donor quaternary ammonium salt
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A novel and effective catalytic system using monobenzylnicotinium chloride combined with copper(i) chloride was employed for the first time in Sonogashira cross-coupling reactions of phenylacetylene with various aryl halides. The goal was to use an efficient green media by using copper instead of palladium in metal-catalyzed coupling reactions. Monobenzyl nicotinium chloride, a quaternary ammonium salt containing a coordinating centre, plays an important role in this catalytic system and increases the efficiency of Cu(i) species during the reaction. A number of internal alkynes were produced in moderate to excellent yields in short reaction times in DMF at 135-140 °C. The efficiency of this catalytic system was compared with the copper-based catalyst obtained from dibenzylnicotinium chloride which has no N-donor active site, wherein lower activity was observed due to lack of a coordination site.
- Hajipour, Abdol Reza,Boostani, Elaheh,Mohammadsaleh, Fatemeh
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p. 94369 - 94374
(2015/11/17)
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- Position of substitution: A facile way to tune the spectroscopic properties of dimethylamino-substituted arylene-ethynylenes
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A series of dimethylamino-substituted arylene-ethynylenes were synthesised by Sonogashira coupling reactions and characterised by the methods of 1H, 13C NMR, UV-Vis, fluorescence, HRMS and theoretical calculations. Effects on spectroscopic properties caus
- Fang, Jing-Kun,Sun, Tengxiao,Fang, Yu,Xu, Zhimin,Zou, Hui,Liu, Yuan,Ge, Fangting
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p. 487 - 491
(2015/11/03)
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- Melamine-based microporous network polymer supported palladium nanoparticles: A stable and efficient catalyst for the sonogashira coupling reaction in water
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A template consisting of a melamine-based microporous polymer network was synthesized and utilized as a solid support to stabilize palladium nanoparticles; the resulting Pd/SNW1 material showed good catalytic activity in copper-free Sonogashira coupling in water. Various aryl iodides were efficiently coupled with arylacetylenes under very low catalyst loadings in an environmentally benign medium. Hot filtration tests confirmed the heterogeneity of the catalyst, which was reused under the optimized conditions without any significant change in its activity. This simple preparation of the catalyst, the stability of the catalyst, product selectivity, and easy recovery and regeneration indicate the possible utilization of this catalytic system in a multitude of catalyzed reactions and industrial processes. Networking possibilities: A template consisting of melamine-based microporous polymer network is synthesized and utilized as a solid support to stabilize palladium nanoparticles; the resulting Pd/SNW1 material shows good catalytic activity in copper-free Sonogashira coupling in water. Various aryl iodides are efficiently coupled with arylacetylenes under very low catalyst loadings in an environmentally benign medium.
- Shunmughanathan, Murugesan,Puthiaraj, Pillaiyar,Pitchumani, Kasi
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p. 666 - 673
(2015/03/05)
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- Multifunctional and robust covalent organic framework-nanoparticle hybrids
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Highly dispersed Pd(0) nanoparticles were successfully immobilized into a stable, crystalline and porous covalent organic framework (COF), TpPa-1, by a solution infiltration method using NABH4 as a reducing agent. High resolution and dark field TEM images confirmed the uniform loading of the Pd(0) nanoparticles into the TpPa-1 matrix without aggregation. This hybrid material exhibited excellent catalytic activity towards the Cu free Sonogashira, Heck and sequential one pot Heck-Sonogashira cross-coupling reactions under basic conditions, and with superior performance compared to commercially available Pd supported on activated charcoal (i.e., 1, 5 and 10 wt%). Additionally, the precursor Pd(ii)-doped COF also displayed competitive catalytic activity for the intramolecular oxidative biaryl synthesis under acidic conditions. Both catalysts were found to be highly stable under the reaction conditions showing negligible metal leaching, non-sintering behavior, and good recyclability. To the best of our knowledge, the organic support used in this work, TpPa-1, constitutes the first COF matrix that can hold both Pd(0) nanoparticles and Pd(ii) complex without aggregation for catalytic purposes under both highly acidic and basic conditions. This journal is the Partner Organisations 2014.
- Pachfule, Pradip,Panda, Manas K.,Kandambeth, Sharath,Shivaprasad,Diaz, David Diaz,Banerjee, Rahul
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p. 7944 - 7952
(2014/05/20)
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- Sonogashira reactions catalyzed by a new and efficient copper(I) catalyst incorporating N-benzyl DABCO chloride
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A new and effective catalytic system using [N-benzyl DABCO] +[Cu4Cl5]- was developed for the palladium-free Sonogashira cross-coupling reactions of phenylacetylene with a variety of aryl halides. In this homogeneous catalytic system, 1-benzyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride, a quaternary ammonium salt containing a coordinating center, plays an important role and increases the efficiency of Cu(I) species during the reaction. A number of internal alkynes were produced in moderate to excellent yields, in short reaction times in DMF at 135 °C.
- Hajipour, Abdol R.,Mohammadsaleh, Fatemeh
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p. 3459 - 3462
(2014/06/10)
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- Copper-catalyzed highly selective semihydrogenation of non-polar carbon-carbon multiple bonds using a silane and an alcohol
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A copper catalyst bearing a suitable Xantphos derivative or NHC ligand was found to be highly efficient for the selective semihydrogenation of non-polar unsaturated compounds using a mixture of a silane and an alcohol as reducing agent. The catalytic system was useful for the selective semihydrogenation of internal alkynes to (Z)-alkenes with suppression of overreduction to the corresponding alkanes. Furthermore, semihydrogenations of terminal alkyne, 1,2-diene, 1,3-diene, 1,3-enyne and 1,3-diyne systems were also achieved selectively. Copyright
- Semba, Kazuhiko,Fujihara, Tetsuaki,Xu, Tinghua,Terao, Jun,Tsuji, Yasushi
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supporting information; experimental part
p. 1542 - 1550
(2012/08/08)
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- CuI-catalyzed Suzuki coupling reaction of organoboronic acids with alkynyl bromides
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A CuI-catalyzed Suzuki cross-coupling reaction of organoboron derivatives with alkynyl bromides has been developed. In the presence of CuI (10 mol %) and 8-hydroxyquinoline (20 mol %), organoboron derivatives including aromatic and alkenyl boronic acids, potassium aryltrifluoroborates, and sodium tetraphenylborate reacted smoothly with 1-bromo-2-substituted acetylene to generate the corresponding cross-coupling products in good to excellent yields in C2H5OH. It is important to note that aromatic N,O-ligand 8-hydroxyquinoline is the most effective ligand for the reaction.
- Wang, Shihua,Wang, Min,Wang, Lei,Wang, Bo,Li, Pinhua,Yang, Jin
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experimental part
p. 4800 - 4806
(2011/07/31)
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- An efficient and recyclable magnetic-nanoparticle-supported palladium catalyst for the suzuki coupling reactions of organoboronic acids with alkynyl bromides
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A highly active, air- and moisture-stable and easily recoverable magnetic-nanoparticle-supported palladium catalyst has been developed for the Suzuki cross-coupling reaction of organoboron derivatives with alkynyl bromides. In the presence of palladium catalyst (0.5 mol%), organoboron derivatives including aromatic and aliphatic boronic acids, potassium aryltrifluoroborates, and sodium tetraphenylborate reacted smoothly with 1-bromo-2-substituted acetylenes to generate the corresponding cross-coupling products in good to excellent yields in ethanol. In addition, it is possible to recover and reuse the supported palladium catalyst at least 16 times without significant loss of its catalytic activity. Georg Thieme Verlag Stuttgart - New York.
- Zhang, Xiuli,Li, Pinhua,Ji, Yong,Zhang, Lei,Wang, Lei
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experimental part
p. 2975 - 2983
(2011/10/19)
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- Fluoro-substituted phenyleneethynylenes: Acetylenic n-type organic semiconductors
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Fluoro-substituted phenyleneethynylenes are synthesized by Sonogashira coupling and acetylide-nucleophilic substitution of fluorobenzenes. Fluoro-substitution of benzenes enables deep LUMO potential, and CF 3-substitution provides high electron
- Matsuo, Daisuke,Yang, Xin,Hamada, Akiko,Morimoto, Kyo,Kato, Takuji,Yahiro, Masayuki,Adachi, Chihaya,Orita, Akihiro,Otera, Junzo
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scheme or table
p. 1300 - 1302
(2011/02/17)
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- Synthesis and spectroscopic study of diphenylamino-substituted phenylene-(poly)ethynylenes: remarkable effect of acetylenic conjugation modes
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A series of diphenylamino-substituted phenylene-(poly)ethynylenes were successfully synthesized by a combination of Sonogashira coupling and double elimination protocol of β-substituted sulfones. When UV-light was irradiated, the amino-substituted phenylene-(poly)ethynylene emitted strong luminescence. The emission underwent a large bathochromic shift in polar solvent because of stabilization of their charge-separated excited states. Analyses of fluorescence life times of aminoacetylenes revealed that radiationless process was suppressed in the polar solvent CH2Cl2, resulting in high quantum yields.
- Fang, Jing-Kun,An, De-Lie,Wakamatsu, Kan,Ishikawa, Takeharu,Iwanaga, Tetsuo,Toyota, Shinji,Matsuo, Daisuke,Orita, Akihiro,Otera, Junzo
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supporting information; experimental part
p. 917 - 920
(2010/05/03)
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- Solvent-free Sonogashira coupling reaction via high speed ball milling
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Herein, we report on the solvent-free Sonogashira reaction utilizing high speed ball milling. Sonogashira coupling of a variety of para substituted aryl halides were performed with trimethylsilylacetylene or phenylacetylene. We observed that iodo and bromo substituted aromatics successfully undergo Sonogashira coupling. However, chloro and fluoro substituted aryl compounds were unreactive. Conducting the coupling reaction in the absence of copper iodide led to low yields. Alternately, if the reaction is conducted with a copper ball in a copper vial in lieu of copper iodide, the coupling product is observed in high yields. This demonstrates the first report on the use of the vial and ball material as a catalyst in a ball milled chemical reaction. The Royal Society of Chemistry 2009.
- Fulmer, Dennis A.,Shearouse, William C.,Medonza, Shareika T.,MacK, James
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experimental part
p. 1821 - 1825
(2011/02/24)
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- Electrical properties of 1,4-bis(4-(phenylethynyl)phenylethynyl)benzene and its application for organic light emitting diodes
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We found that a phenylene ethynylene derivative, 1,4-bis(4-(phenylethynyl) phenylethynyl)benzene (BPPB), provides very high photoluminescence efficiency both in solution (ΦPL = 95 ± 3%) and thin films (ΦPL = 71 ± 3%); further, we observed blue electroluminescence (EL) of λEL (max) ~470 and 510 nm with an external EL efficiency of ηEL ~0.53% and maximum luminance of ~70000 cd m-2 at current density of ~2 A cm -2 with BPPB as an emitter; also we identified that BPPB functions as a hole transport layer in organic light emitting diodes. The Royal Society of Chemistry.
- Fenenko, Larysa,Shao, Guang,Orita, Akihiro,Yahiro, Masayuki,Otera, Junzo,Svechnikov, Sergei,Adachi, Chihaya
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p. 2278 - 2280
(2007/12/27)
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- Synthesis of bis(phenylethynyl)arylene-linked diporphyrins designed for studies of intramolecular energy transfer
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A series of donor-bridge-acceptor systems has been designed to give information on how the medium between the donor and the acceptor influences the excitation energy transfer process. The donor and the acceptor are zinc and free base porphyrins, respectiv
- Kajanus,Van Berlekom,Albinsson,Martensson
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p. 1155 - 1162
(2007/10/03)
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- Palladium-catalyzed cross-coupling of organostannanes with iodanes
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The palladium-catalyzed coupling of organostannanes with iodanes (Koser's and Zefirov's reagents) in the presence of palladium catalyst was accomplished at room temperature under aqueous conditions to afford phenyl- or 4-iodophenyl-substituted products depending on the iodanes used.
- Kang, Suk-Ku,Lee, Hong-Woo,Kim, Jae-Sun,Choi, Sang-Chul
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p. 3723 - 3726
(2007/10/03)
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