13238-38-5Relevant articles and documents
"Click" dendrimer-stabilized palladium nanoparticles as a green catalyst down to parts per million for efficient C-C cross-coupling reactions and reduction of 4-nitrophenol
Deraedt, Christophe,Salmon, Lionel,Astruc, Didier
, p. 2525 - 2538 (2014)
The concept of the nanoreactor valuably contributes to catalytic applications of supramolecular chemistry. Therewith molecular engineering may lead to organic transformations that minimize the amount of metal catalyst to reach the efficiency of enzymatic catalysis. The design of the dendritic nanoreactor proposed here involves hydrophilic triethylene glycol (TEG) termini for solubilization in water and water/ethanol mixed solvents combined with a hydrophobic dendritic interior containing 1,2,3-triazole ligands that provide smooth stabilization of very small (1 to 2nm) palladium nanoparticles (PdNPs). The PdNPs stabilized in such nanoreactors are extraordinarily active in water/ethanol (1/1) for the catalysis of various carbon-carbon coupling reactions (Suzuki-Miyaura, Heck and Sonogashira) of aryl halides down to sub-ppm levels for the Suzuki-Miyaura coupling of aryl iodides and aryl bromides. The reduction of 4-nitrophenol to 4-aminophenol in water also gives very impressive results. The difference of reactivity between the two distinct dendrimers with, respectively, 27 (G0) and 81 (G1) TEG termini is assigned to the difference of PdNP core size, the smaller G0 PdNP core being more reactive than the G1 PdNP core (1.4 vs. 2.7nm), which is also in agreement with the leaching mechanism.
Dialyzable carbosilane dendrimers as soluble supports for the functionalization of pyridine fragments via palladium-catalyzed coupling reactions
Le Notre, Jerome,Firet, Judith J.,Sliedregt, Leo A. J. M.,Van Steen, Bart J.,Van Koten, Gerard,Gebbink, Robertus J. M. Klein
, p. 363 - 366 (2005)
(Chemical Equation Presented) The use of carbosilane (CS) dendrimers as soluble supports in liquid phase organic synthesis (LPOS) is described. Control of the three key steps is perfectly achieved by covalently binding a pyridine fragment to the soluble s
MCM-41-immobilized Schiff base-pyridine bidentate copper(I) complex as a highly efficient and recyclable catalyst for the Sonogashira reaction
Zhao, Hong,Huang, Bin,Wu, Yichao,Cai, Mingzhong
, p. 21 - 28 (2015)
Abstract A novel MCM-41-immobilized Schiff base-pyridine bidentate copper(I) complex [MCM-41-Sb,Py-CuI] was conveniently prepared from commercially available and inexpensive 3-aminopropyltriethoxysilane via immobilization on MCM-41, followed by reacting w
Sustainable Ligand-Free Heterogeneous Palladium-Catalyzed Sonogashira Cross-Coupling Reaction in Deep Eutectic Solvents
Messa, Francesco,Dilauro, Giuseppe,Perna, Filippo M.,Vitale, Paola,Capriati, Vito,Salomone, Antonio
, p. 1979 - 1984 (2020)
The commercially available and cheap Pd/C was found to promote Sonogashira couplings in the environmentally friendly choline chloride/glycerol eutectic mixture in the absence of external ligands. Under heterogeneous conditions, (hetero)aryl iodides were successfully coupled with both aromatic and aliphatic alkynes in yields ranging from 50 to 99 % within 3 h at 60 °C. The aforementioned catalytic system proved to be effective also towards electron-rich iodides, which are notoriously known to be poorly reactive in Pd-catalyzed Sonogashira coupling reactions. The eutectic mixture and the catalyst could easily and successfully be recycled up to four times with an E-factor as low as 24.4.
Palladium-phosphinous acid-catalyzed Sonogashira cross-coupling reactions in water
Wolf, Christian,Lerebours, Rachel
, p. 2161 - 2164 (2004)
A palladium-phosphinous acid-catalyzed Sonogashira cross-coupling reaction that proceeds in water under air atmosphere in the absence of organic co-solvents has been developed. Disubstituted alkynes have been prepared in up to 91% yield by POPd-catalyzed
Alkynyl?B(dan)s in Various Palladium-Catalyzed Carbon?Carbon Bond-Forming Reactions Leading to Internal Alkynes, 1,4-Enynes, Ynones, and Multiply Substituted Alkenes
Tani, Tomohiro,Sawatsugawa, Yuuki,Sano, Yusuke,Hirataka, Yo,Takahashi, Naomi,Hashimoto, Sadahiro,Sugiura, Tetsuya,Tsuchimoto, Teruhisa
, p. 1815 - 1834 (2019)
It was found that the C(sp)?B(dan) bond of alkynyl?B(dan)s can be directly used for palladium-catalyzed carbon?carbon bond-forming reactions with aryl(alkenyl) halides and allylic carbonates as electrophiles, thus delivering unsymmetrical internal alkynes and unconjugated 1,4-enynes, respectively. With acyl chlorides as electrophiles, ynone synthesis is also promoted by a palladium catalyst with the assistance of a copper co-catalyst. These reactions can be achieved as more convenient one-pot reactions, without isolating the alkynyl?B(dan) formed in situ by the zinc-catalyzed dehydrogenative borylation of alkynes with HB(dan). In addition to direct C(sp)?B(dan) bond transformations, the C≡C bond in an alkynyl?B(dan) proved to be a promising scaffold for the construction of a multisubstituted alkene, which is synthesized by diboration of the C≡C?B(dan) moiety, leading to a triborylalkene followed by iterative regio- and stereoselective Suzuki?Miyaura cross-coupling reactions. As one example, the synthesis of the ethene with four different aryl groups, p-MeC6H4, p-MeOC6H4, p-NCC6H4, and p-F3CC6H4, was attained in high overall yield of 64% in six steps starting from the terminal alkyne, p-MeC6H4C≡CH. Besides these synthetic applications of the alkynyl?B(dan), the scope of the alkynyl substrate in the zinc-catalyzed dehydrogenative borylation was expanded to enhance the reliability as a provider of the alkynyl?B(dan). Consequently, 42 alkynes were found to participate in the dehydrogenative borylation as substrates; these are alkyl-, alkenyl-, aryl-, heteroaryl-, ferrocenyl-, silyl-, and borylalkynes, with or without a variety of functional groups. Lastly, a new method for preparing HB(dan), as a sulfide-free, cost-saving, and reaction-time-saving route, is disclosed. (Figure presented.).
Palladium Nanoparticles Immobilized on Individual Calcium Carbonate Plates Derived from Mussel Shell Waste: An Ecofriendly Catalyst for the Copper-Free Sonogashira Coupling Reaction
Saetan, Trin,Lertvachirapaiboon, Chutiparn,Ekgasit, Sanong,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
, p. 2221 - 2230 (2017)
The conversion of waste into high-value materials is considered an important sustainability strategy in modern chemical industries. A large volume of shell waste is generated globally from mussel cultivation. In this work, mussel shell waste (Perna viridis) is transformed into individual calcium carbonate plates (ICCPs) and is applied as a support for a heterogeneous catalyst. Palladium nanoparticles (3–6 nm) are deposited with an even dispersion on the ICCP surface, as demonstrated by X-ray diffraction and scanning electron microscopy. Using this system, Sonogashira cross-coupling reactions between aryl iodides and terminal acetylenes were accomplished in high yields with the use of 1 % Pd/ICCP in the presence of potassium carbonate without the use of any copper metal or external ligand. The Pd/ICCP catalyst could also be reused up to three times and activity over 90 % was maintained with negligible Pd-metal leaching. This work demonstrates that mussel shell waste can be used as an inexpensive and effective support for metal catalysts in coupling reactions, as demonstrated by the successful performance of the Pd-catalyzed, copper-free Sonogashira cross-coupling process.
Copper- and amine-free sonogashira-hagihara coupling reaction catalyzed by Pd(0) nanoparticles supported on modified crosslinked polyacrylamide
Tamami, Bahman,Ghasemi, Soheila
, p. 1967 - 1978 (2011)
Pd(0) nanoparticles supported on modified crosslinked polyacrylamide containing phosphinite ligand was prepared. The complex was a highly efficient catalyst for the Sonogashira- Hagihara coupling reaction in the absence of a copper cocatalyst and an amine
Magnetite (Fe3O4) nanoparticles-catalyzed Sonogashira- Hagihara reactions in ethylene glycol under ligand-free conditions
Firouzabadi, Habib,Iranpoor, Nasser,Gholinejad, Mohammad,Hoseini, Jafar
, p. 125 - 132 (2011)
A novel application of nanoparticles of paramagnetic magnetite (Fe 3O4) as an efficient catalyst for carbon-carbon bond formation via the Sonogashira-Hagihara reaction under heterogeneous ligand-free conditions in ethylene glycol (EG) is described. By using this catalyst, arylalkynes are produced from the reaction of aryl iodides and activated heteroaryl bromides with alkynes. The results are reproducible using the catalyst, which was prepared from different sources. The catalyst is easily separated by an external magnetic field from the reaction mixture. The separated catalyst can be recycled for several consecutive runs without appreciable loss of its catalytic activity.
Pd supported on clicked cellulose-modified magnetite-graphene oxide nanocomposite for C-C coupling reactions in deep eutectic solvent
Karimi, Sabah,Masteri-Farahani, Majid,Niakan, Mahsa,Shekaari, Hemayat
, (2020/10/02)
Cellulose-modified magnetite-graphene oxide nanocomposite was prepared via click reaction and utilized for immobilization of palladium (Pd) nanoparticles without using additional reducing agent. The abundant OH groups of cellulose provided the uniform dispersion and high stability of Pd nanoparticles, while magnetite-graphene oxide as a supporting material offered high specific surface area and easy magnetic separation. The as-prepared nanocomposite served as a heterogeneous catalyst for the Heck and Sonogashira coupling reactions in various hydrophilic and hydrophobic deep eutectic solvents (DESs) as sustainable and environmentally benign reaction media. Among the fifteen DESs evaluated for coupling reactions, the hydrophilic DES composed of dimethyl ammonium chloride and glycerol exhibited the best results. Due to the low miscibility of catalyst and DES in organic solvents, the separated aqueous phase containing both of the catalyst and DES can be readily recovered by evaporating water and retrieved eight times with negligible loss of catalytic performance.
Aerobic Cu and amine free Sonogashira and Stille couplings of aryl bromides/chlorides with a magnetically recoverable Fe3O4@SiO2 immobilized Pd(II)-thioether containing NHC
Khandaka, Himanshu,Sharma, Kamal Nayan,Joshi, Raj Kumar
supporting information, (2021/02/20)
Two value added C–C cross coupling reactions; Sonogashira and Stille couplings were achieved at milder conditions in the catalytic presence of a magnetically recoverable heterogeneous catalyst Fe3O4@SiO2@NHC^SPh-Pd(II). The catalyst was earlier reported for Suzuki-Miyaura reaction, and as an extension of its catalytic efficiency, the Stille and Sonogashira cross coupling reactions under aerobic condition has been explored in present report. The Sonogashira coupling of aryl bromides and terminal alkynes produced an excellent yield (~96% at 0.25 mol% Pd) of the desired coupling product under copper and amines free conditions. Moreover, an excellent Stille coupling of readily available and more latent aryl chlorides and trialkylstannane was obtained (yields up to 95% at 0.25 mol% Pd) in absence of toxic fluorides additives. The broad substrate scope of the catalyst for both the coupling reactions and the magnetically recoverable feature of catalyst make this reaction highly desirable for industrial applications of present heterogeneous catalysis.
Palladium-catalyzed decarbonylative sonogashira coupling of terminal alkynes with carboxylic acids
Chen, Tieqiao,Huang, Tianzeng,Li, Chunya,Li, Wenhui,Li, Xinyi,Li, Zhaohui,Liu, Long,Tang, Zhi,Zhang, Tao
supporting information, p. 3304 - 3309 (2021/05/31)
A direct decarbonylative Sonogashira coupling of terminal alkynes with carboxylic acids was achieved through palladium catalysis. This reaction did not use overstoichiometric oxidants, thus overcoming the homocoupling issue of terminal alkynes. Under the reaction conditions, a wide range of carboxylic acids including those bioactive ones could couple readily with various terminal alkynes, thus providing a relative general method for preparing internal alkynes.
