Copper-Impregnated Magnetite as a Heterogeneous Catalyst for the Homocoupling of Terminal Alkynes

Copper-impregnated magnetite is a versatile heterogeneous catalytic system for the synthesis of 1,3-diynes by the homocoupling of terminal alkynes. This catalyst does not require the use of pressurized oxygen as the oxidant and it does not need a solvent or harsh conditions to give the expected products. Moreover, the catalyst can be removed from the reaction medium simply by using a magnet. The reaction occurs at the lowest copper loading reported for any heterogeneous catalyst.

Catalyzed addition of acid chlorides to alkynes by unmodified nano-powder magnetite: synthesis of chlorovinyl ketones, furans, and related cyclopentenone derivatives

Inexpensive and commercially available nano-powder magnetite is an excellent catalyst for the addition of acid chlorides to internal and terminal alkynes, yielding the corresponding chlorovinyl ketones in good yields. The process has been applied to the synthesis of 5-chloro-4-arylcyclopent-2-enones, 3-aryl-1H-cyclopenta[a]naphthalen-1-ones, and (E)-3-alkylidene-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-ones, just by changing the nature of the starting acid chloride or the alkyne. All tested processes elapse with an acceptable or excellent regio- and stereo-selectivity. Moreover, the use of the iridium impregnated on magnetite catalyst permits the integration of the chloroacylation process with a second dehydrochlorination–annulation process to yield, in one-pot, 1-aryl-2,4-dialkylfurans in good yields, independently of the nature of the starting reagents, and including the heteroaromatic ones.

Multicomponent Azide-Alkyne Cycloaddition Catalyzed by Impregnated Bimetallic Nickel and Copper on Magnetite

A new bimetallic catalyst derived from nickel and copper has been used successfully for the first time in the multicomponent reaction of terminal alkynes, sodium azide, and benzyl bromide derivatives. The presence of both metallic species on the surface of magnetite seems to have a positive and synergetic effect. The catalyst loading is the lowest ever published for a catalyst of copper anchored on any type of iron support. The catalyst could be easily removed from the reaction media just by magnetic decantation and it could be reused up to ten times without any negative effect on the initial results.

Copper-Free Oxime–Palladacycle-Catalyzed Sonogashira Alkynylation of Deactivated Aryl Bromides and Chlorides in Water under Microwave Irradiation

Palladium-catalyzed Heck alkynylation cross-coupling reactions between terminal alkynes and deactivated aryl chlorides and aryl bromides can be performed in the absence of copper cocatalyst with water as solvent at 130 °C under microwave irradiation. An oxime-derived chloro-bridged palladacycle is an efficient precatalyst for this transformation with 2-dicyclohexylphosphanyl-2′,4′,6′-triisopropylbiphenyl (XPhos) as ancillary ligand, pyrrolidine as base, and SBDS as surfactant. All of the reactions can be performed under air and with reagent-grade chemicals under low loading conditions (0.1–1 mol-% Pd).

Synthesis of Dihydroisobenzofurans via Palladium-Catalyzed Sequential Alkynylation/Annulation of 2-Bromobenzyl and 2-Chlorobenzyl Alcohols under Microwave Irradiation

The palladium-catalyzed synthesis of dihydroisobenzofurans has been performed by sequential Sonogashira cross-coupling/cyclization reactions between terminal alkynes and 2-(hydroxymethyl)bromo- and chlorobenzenes in methanol as solvent at 130 °C under microwave irradiation. A 4,4′-dichlorobenzophenone oxime-derived chloro-bridged palladacycle is an efficient pre-catalyst to perform this tandem process using 2-dicyclohexylphosphanyl-2′,4′,6′-triisopropylbiphenyl (Xphos) as ancillary ligand and potassium hydroxide as base in the absence of a copper cocatalyst. Under these conditions, functionalized 2-bromo- and 2-chlorobenzaldehydes are also suitable partners in the domino process affording phthalans in good yields. All the reactions can be performed under air and employing reagent-grade chemicals under low loading conditions (1 mol% Pd).

Nanoparticles of tungsten as low-cost monometallic catalyst for selective hydrogenation of 3-hexyne

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Copper Nanoparticles in Click Chemistry

Conspectus: The challenges of the 21st century demand scientific and technological achievements that must be developed under sustainable and environmentally benign practices. In this vein, click chemistry and green chemistry walk hand in hand on a pathway of rigorous principles that help to safeguard the health of our planet against negligent and uncontrolled production. Copper-catalyzed azide–alkyne cycloaddition (CuAAC), the paradigm of a click reaction, is one of the most reliable and widespread synthetic transformations in organic chemistry, with multidisciplinary applications. Nanocatalysis is a green chemistry tool that can increase the inherent effectiveness of CuAAC because of the enhanced catalytic activity of nanostructured metals and their plausible reutilization capability as heterogeneous catalysts. This Account describes our contribution to click chemistry using unsupported and supported copper nanoparticles (CuNPs) as catalysts prepared by chemical reduction. Cu(0)NPs (3.0 ± 1.5 nm) in tetrahydrofuran were found to catalyze the reaction of terminal alkynes and organic azides in the presence of triethylamine at rates comparable to those achieved under microwave heating (10–30 min in most cases). Unfortunately, the CuNPs underwent dissolution under the reaction conditions and consequently could not be recovered. Compelling experimental evidence on the in situ generation of highly reactive copper(I) chloride and the participation of copper(I) acetylides was provided. The supported CuNPs were found to be more robust and efficient catalyst than the unsupported counterpart in the following terms: (a) the multicomponent variant of CuAAC could be applied; (b) the metal loading could be substantially decreased; (c) reactions could be conducted in neat water; and (d) the catalyst could be recovered easily and reutilized. In particular, the catalyst composed of oxidized CuNPs (Cu2O/CuO, 6.0 ± 2.0 nm) supported on carbon (CuNPs/C) was shown to be highly versatile and very effective in the multicomponent and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles in water from organic halides as azido precursors; magnetically recoverable CuNPs (3.0 ± 0.8 nm) supported on MagSilica could be alternatively used for the same purpose under similar conditions. Incorporation of an aromatic substituent at the 1-position of the triazole could be accomplished using the same CuNPs/C catalytic system starting from aryldiazonium salts or anilines as azido precursors. CuNPs/C in water also catalyzed the regioselective double-click synthesis of β-hydroxy-1,2,3-triazoles from epoxides. Furthermore, alkenes could be also used as azido precursors through a one-pot CuNPs/C-catalyzed azidosulfenylation–CuAAC sequential protocol, providing β-methylsulfanyl-1,2,3-triazoles in a stereo- and regioselective manner. In all types of reaction studied, CuNPs/C exhibited better behavior than some commercial copper catalysts with regard to the metal loading, reaction time, yield, and recyclability. Therefore, the results of this study also highlight the utility of nanosized copper in click chemistry compared with bulk copper sources.

Microwave-assisted palladium-catalyzed highly regio- and stereoselective head to head dimerization of terminal aryl alkynes in water

A highly regio- and stereoselective oxime palladacycle/imidazolinium-catalyzed head to head dimerization of terminal aryl alkynes in water is presented. The reaction, which is carried out at 130 °C under microwave irradiation in the presence of 1,3-bis-(2,6-diisopropylphenyl)imidazolinium chloride as ligand, triethylamine as base, and TBAB as surfactant, allows the synthesis of (E)-1,4-enynes as single stereoisomers in good isolated yields.

Actitudes de los profesionales de Enfermería hacia el enfermo crónico y terminal

Hemos estudiado una muestra (n=IOO) de profesionales de enfermería de las provincias de Alicante y Valencia, analizando las actitudes, según el modelo de Ajzen y Fishbein, con respecto a dos grupos de enfermos: crónicos y terminales. En general las actitudes de estos profesionales son bastante positivas en ambos casos y en todos su s componentes; aunque encontramos como hecho más destacado una tendencia actitudinal más baja significativamente hacia el enfermo terminal en sus componentes afectivo y comportamental.

Solvent- and Ligand-free Diboration of Alkynes and Alkenes Catalyzed by Platinum Nanoparticles on Titania

Platinum nanoparticles supported on titania efficiently catalyzed the diboration of alkynes and alkenes under solvent- and ligand-free conditions in air. The cis-1,2-diborylalkenes and 1,2-diborylalkanes were obtained in moderate to excellent yields following, in most cases, a simple filtration workup protocol. The versatility of the cis-1,2-diboronvinyl compounds was demonstrated in a series of organic transformations, including the Suzuki–Miyaura cross coupling and the boron–halogen exchange.

Direct synthesis of β-ketophosphonates and vinyl phosphonates from alkenes or alkynes catalyzed by CuNPs/ZnO

Copper nanoparticles (CuNPs) supported on ZnO have been shown to effectively catalyze the direct synthesis of β-ketophosphonates from alkenes or alkynes, and that of vinyl phosphonates from alkynes and diethylphosphite, under air and in the absence of any additive or ligand. When using alkynes as starting materials, the selectivity proved to be dependent on the nature of the alkyne. Thus, alkynes conjugated with an aromatic ring or a carbon–carbon double bond gave β-ketophosphonates as the main reaction products, whereas aliphatic alkynes or alkynes conjugated with a carbonyl group led to the formation of the corresponding vinyl phosphonates.