10008-73-8Relevant articles and documents
Self-assembled M12L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction
Gonell, Sergio,Caumes, Xavier,Orth, Nicole,Ivanovi?-Burmazovi?, Ivana,Reek, Joost. N. H.
, p. 1316 - 1321 (2019)
The application of large M12L24 nanospheres allows the pre-concentration of catalysts to reach high local concentrations, facilitating reactions that proceed through dinuclear mechanisms. The mechanism of the copper(i)-catalyzed cyclization of 4-pentynoic acid has been elucidated by means of a detailed mechanistic study. The kinetics of the reaction show a higher order in copper, indicating the formation of a bis-Cu intermediate as the key rate determining step of the reaction. This intermediate was further identified during catalysis by CIS-HRMS analysis of the reaction mixture. Based on the mechanistic findings, an M12L24 nanosphere was applied that can bind up to 12 copper catalysts by hydrogen bonding. This pre-organization of copper catalysts in the nanosphere results in a high local concentration of copper leading to higher reaction rates and turnover numbers as the dinuclear pathway is favored.
"water soluble" palladium nanoparticle engineering for C-C coupling, reduction and cyclization catalysis
Iben Ayad,Belda Marín,Colaco,Lefevre,Méthivier,Ould Driss,Landoulsi,Guénin
, p. 6646 - 6657 (2019)
The use of Pd nanoparticles (Pd-NPs) to realize several important organic reactions allows efficient catalysis with low metal loading (1000 ppm), hence providing a greener catalytic system. However, to be truly green Pd-NPs need to be synthesized in a sustainable manner and be able to react in aqueous media in order to avoid the use of organic solvents. Here we describe an original and eco-friendly synthesis of Pd-NPs (using benign reactants and simple conditions) perfectly stable in water. Remarkably, this synthesis allows for control over their size and morphology by simply tuning the pH of the stabilizer. We then evaluate the catalytic efficiency of these Pd-NPs on six different model reactions (Suzuki Miyaura, Sonogashira, Heck, nitrophenol reduction and pentynoic cycloisomerization) in aqueous media. We show that the stabilizer structure influences the activity owing to its ability to promote the mass transfer of the organic substrates towards the NP surface in the aqueous environment. Finally, catalytic evaluations show that our nano-catalysts prepared in an eco-friendly manner are among the best catalysts described so far in the literature in each case, with high turnover frequencies reached with a low loading of palladium.
PALLADIUM(II) CATALYZED CYCLIZATION OF ALKYNOIC ACIDS
Lambert, Claude,Utimoto, Kiitiro,Nozaki, Hitosi
, p. 5323 - 5326 (1984)
Under the catalytic action of palladium(II) in the presence of triethylamine, 3-, 4-, and 5-alkynoic acids afford 3-buten-4-olides, 4-penten-4-olides,and 5-hexen-5-olide, respectively, in good to excellent yields.
Metal-ligand cooperation in the cycloisomerization of alkynoic acids with indenediide palladium pincer complexes
Nebra, Noel,Monot, Julien,Shaw, Rosie,Martin-Vaca, Blanca,Bourissou, Didier
, p. 2930 - 2934 (2013)
Indenediide Pd complexes 1a-c are shown to very efficiently catalyze the cycloisomerization of alkynoic acids into alkylidene lactones via metal-ligand cooperation (TON up to 2000). Complexes 1a-c are competent toward a broad range of alkynoic acids, including functionalized and internal ones, and give access to 5- as well as 6- and 7-membered lactones in excellent yields and with very high selectivities.
Cyclisations of alkynoic acids using copper(I) arylspiroborate complexes
Lee, Graham M.,Bowes, Eric G.,Vogels, Christopher M.,Decken, Andreas,Westcott, Stephen A.
, p. 2106 - 2112 (2019)
In this study we have studied the synthesis, characterization and catalytic activity of phosphinocopper(I) complexes [Cu(PPh3)3(NCCH3)][B(O2C6H4-4-R)2] (3a: R = H; 3b: R = Me; 3c
Gold Functionalized Platinum M12L24-Nanospheres and Their Application in Cyclization Reactions
Leenders, Stefan H. A. M.,Dürr, Maximillian,Ivanovic-Burmazovic, Ivana,Reek, Joost N. H.
, p. 1509 - 1518 (2016)
Nanospheres can be formed by combining 24 bispyridinyl building blocks with a palladium or platinum precursor. These spheres can be functionalized on the inside with a gold(I) chloride complex leading to a high local concentration of gold(I) complexes. The high local concentration makes the neutral gold species an active catalyst. Furthermore, the platinum-gold spheres can be post-modified with a silver(I) salt to form cationic gold(I) catalysts. The platinum assemblies are demonstrated to be stable in the presence of various substrates and as a result several cyclization reactions have been carried out using these new spheres as catalysts. Higher conversions in a [4+2] cycloaddition are observed for the sphere catalyst compared to the mono-nuclear analogues. Also the cyclization of 1,6-enynes can be facilitated by the confined gold catalyst and high activity is observed in the activation of allenes. For the lactonization of alkynoic acids, a different selectivity is observed compared to a standard gold(I) complex, demonstrating that the high local concentration due to a confined space can induce other selectivity in catalysis.
Cyclisation of acetylenic carboxylic acids and acetylenic alcohols to oxygen-containing heterocycles using cationic rhodium(I) complexes
Elgafi, Sarah,Field, Leslie D.,Messerle, Barbara A.
, p. 97 - 104 (2000)
Square planar cationic rhodium(I) dicarbonyl complexes [{Rh((mim)2CH2)(CO)2}+BPh -4] (1) and [{Rh((mBnzim)2CH2)-(CO)2}+BPh -4/su
Synthesis and characterization of oxygen/sulfur-bridged incomplete cubane-type clusters, [M3S4(Tpe)3]+ and [M 3OS3(Tpe)3]+ (M = Mo and W), and a mixed-metal cubane-type cluster, [Mo3
Yoshida, Ryouichi,Shibahara, Takashi,Akashi, Haruo
, p. 839 - 849 (2013)
The reaction of [Mo3S4(H2O) 9]4+(1) and [Mo3OS3(H 2O)9]4+ (2) with hydrotris(pyrazolyl)ethanol (HTpe) ligands produced [Mo3S4/su
Palladium pincer complexes featuring an unsymmetrical SCN indene-based ligand with a hemilabile pyridine sidearm
Brunel, Paul,Lhardy, Chloé,Mallet-Ladeira, Sonia,Monot, Julien,Martin-Vaca, Blanca,Bourissou, Didier
, p. 9801 - 9806 (2019)
A new unsymmetrical indene-based pro-ligand featuring thiophosphinoyle and methylpyridine sidearms 2 was prepared. Coordination and cyclometalation in the presence of [PdCl2(PhCN)2] and PS-DIEA afforded three well-defined 2-indenyl S
Enhanced catalytic performance of indenediide palladium pincer complexes for cycloisomerization: Efficient synthesis of alkylidene lactams
Espinosa-Jalapa, Noel ángel,Ke, Diandian,Nebra, Noel,Le Goanvic, Lucas,Mallet-Ladeira, Sonia,Monot, Julien,Martin-Vaca, Blanca,Bourissou, Didier
, p. 3605 - 3611 (2014)
New SCS Pd pincer complexes featuring a noninnocent indenediide backbone show high catalytic activity in cycloisomerization. A variety of alkylidene lactams (five- to seven-membered rings) have been prepared efficiently from N-tosyl alkynylamides, and goo
