Lanthanide Triflates Research Articles

Gallium(III) Triflate: An Efficient and a Sustainable Lewis Acid Catalyst for Organic Synthetic Transformations

Green chemical processes play a crucial role in sustainable development, and efficient recyclable catalysts that can be conveniently applied in various chemical reactions are the key elements for the development of sustainable synthetic processes. Many organic transformations rely on Lewis and Brønsted acid catalysts, and such molecules have been widely studied in organic synthesis. Over the years, researchers have looked for Lewis acid catalysts that provide high selectivity and high turnover frequency but are also stable in aqueous media and recoverable. Since the first preparation of trifluoromethanesulfonic acid by Hazeldine (triflic acid, HOTf), researchers have synthesized and used numerous metal triflates in a variety of organic reactions. Even though the rare earth metal triflates have played a major role in these studies, the majority of rare earth triflates lack one or more of the primary properties of sustainable catalysts: low cost and easy availability of the metals, easy preparation of triflates, aqueous/thermal stability, recyclability, and catalytic efficiency. In this Account, we describe the synthetic applications of Ga(OTf)(3) and its advantages over similar catalysts. Ga(OTf)(3) can be conveniently prepared from gallium metal or gallium chloride in excess of trifluoromethanesulfonic acid (triflic acid) under reflux. Among many Lewis acid catalysts recently studied, Ga(OTf)(3) is water tolerant and soluble and requires very low catalyst loading to drive various acid-catalyzed reactions including Friedel-Crafts alkylation, hydroxyalkylation, and acylation selectively and efficiently. In many reactions Ga(OTf)(3) demonstrated high chemo- and regioselectivity, high yields, excellent stability, and recyclability. We successfully synthesized many biologically active heterocycles and their fluoroanalogs under mild conditions. Many challenging reactions such as the ketonic Strecker reactions proceed efficiently via Ga(OTf)(3) catalysis. Because it is stable in water, this catalyst provides the opportunity to study substrates and develop new synthetic protocols in aqueous media, significantly reducing the production of hazardous waste from organic solvents and toxic catalyst systems.

Efficient hydroalkoxylation of alkenes to generate octane-boosting ethers using recyclable metal triflates and highly active metal triflate/Brønsted acid-assisted catalysts

gem-Disubstituted alkenes are directly and readily etherified with alcohols using Al(OTf) 3 and Zr(OTf) 4 as recyclable Lewis acid catalysts. In contrast, primary or secondary alkene analogues were inert under these conditions, enabling excellent chemoselectivity. Lanthanide triflates are inactive as catalysts for such reactions, as is phosphoric acid. But a combination of these two otherwise inactive entities led to an ‘assisted acidity’ scenario that saw significant unmatched catalyst activity. All catalysts of this study are recyclable a number of times without loss of activity.

Neodymium triflate modified nafion composite membrane for reduced alcohol permeability in direct alcohol fuel cell

This paper reports an experimental study on the modification of nafion membrane with neodymium triflate, Nd(SO3CF3)3, a rare earth triflate. The triflate ion resembles nafion in structure and has high lewis acidity, high coordination number, hygroscopic nature and thermal stability. These properties make the neodymium triflate (NdTfO) suitable to improve the performance of NdTfO/nafion membranes in direct alcohol fuel cell by reducing fuel permeability without compromising other properties. The NdTfO/nafion membranes reduced alcohol permeability by nearly 48%. The proton conductivity of 1% NdTfO/nafion was increased by at least 24% as compared to pure cast nafion membrane. The mechanical strength of 1% NdTfO/nafion was higher than that of pure cast nafion. The composite membrane was thermally and chemically stable and has potential for use in direct alcohol fuel cells. A DMFC was developed and its performance was evaluated using the composite membrane, which showed encouraging results.

ChemInform Abstract: The Aldol Reaction of Silyl Enol Ethers with Aldehydes in Aqueous Media.

Abstract The aldol reaction of silyl enol ethers with aldehydes is successfully carried out in aqueous media by using a lanthanide trifluoromethanesulfonate as a catalyst. Water soluble aldehydes are applicable and the catalyst can be recovered and reused in this reaction.

ChemInform Abstract: Lewis Acid Catalyzed Reactions in Aqueous Solution.

Rare earth metal trifluoromethanesulfonates (lanthanide and scandium triflates) were found to be stable Lewis acids in water and can act as Lewis acid catalysts in several carbon-carbon forming reactions In all cases, the reactions proceeded smoothly in the presence of a catalytic amount of the triflate under mild conditions in aqueous solution. For example, in the presence of a catalytic amount of rare earth metal triflate, formaldehyde in water solution (commercial formaldehyde solution) was activated and the hydroxymethylation reaction of silyl enol ethers proceeded smoothly Rare earth metal triflates were also quite effective in the aldol reaction of silyl enol ethers with aldehydes in aqueous media, and water-soluble aldehydes such as acetaldehyde, acrolein, and chloroacetaldehyde could be employed for direct use. Moreover, the allylation reaction of a wide variety of carbonyl compounds with tetraallyltin was successfully carried out in aqueous media by using scandium triflate as a catalyst. Unprotected sugars reacted directly to give the adducts in high yields. In all these reactions, lanthanide triflates were quantitatively recovered after the reactions were completed and could be reused.

ChemInform Abstract: Lanthanoid Triflate and Triflide Catalyzed Atom Economic Nitration of Fluoroarenes.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Investigation of Mn(III)-Based Oxidative Free Radical Cyclization Reactions Toward the Synthesis of Triptolide: The Effects of Lanthanoid Triflates and Substituents on Stereoselectivity.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Lanthanoid Triflates Catalyzed Reaction of a Silyl Ynolate with Aldimines.

ChemInform Abstract: Lanthanoid Triflates Catalyzed Reaction of a Silyl Ynolate with Aldimines.

Efficient Intramolecular Hydroalkoxylation of Unactivated Alkenols Mediated by Recyclable Lanthanide Triflate Ionic Liquids: Scope and Mechanism

Lanthanide triflate complexes of the type [Ln(OTf)(3)] (Ln=La, Sm, Nd, Yb, Lu) serve as effective, recyclable catalysts for the rapid intramolecular hydroalkoxylation (HO)/cyclization of primary/secondary and aliphatic/aromatic hydroxyalkenes in imidazolium-based room-temperature ionic liquids (RTILs) to yield the corresponding furan, pyran, spirobicyclic furan, spirobicyclic furan/pyran, benzofuran, and isochroman derivatives. Products are straightforwardly isolated from the catalytic solution, conversions exhibit Markovnikov regioselectivity, and turnover frequencies are as high as 47 h(-1) at 120 degrees C. The ring-size rate dependence of the primary alkenol cyclizations is 5>6, consistent with a sterically controlled transition state. The hydroalkoxylation/cyclization rates of terminal alkenols are slightly more rapid than those of internal alkenols, which suggests modest steric demands in the cyclic transition state. Cyclization rates of aryl-functionalized hydroxyalkenes are more rapid than those of the linear alkenols, whereas five- and five/six-membered spirobicyclic skeletons are also regioselectively closed. In cyclization of primary, sterically encumbered alkenols, turnover-frequency dependence on metal-ionic radius decreases by approximately 80-fold on going from La(3+) (1.160 A) to Lu(3+) (0.977 A), presumably reflecting steric impediments along the reaction coordinate. The overall rate law for alkenol hydroalkoxylation/cyclization is v approximately k[catalyst](1)[alkenol](1). An observed ROH/ROD kinetic isotope effect of 2.48 (9) is suggestive of a catalytic pathway that involves kinetically significant intramolecular proton transfer. The present activation parameters--enthalpy (DeltaH(++))=18.2 (9) kcal mol(-1), entropy (DeltaS(++))=-17.0 (1.4) eu, and energy (E(a))=18.2 (8) kcal mol(-1)--suggest a highly organized transition state. Proton scavenging and coordinative probing results suggest that the lanthanide triflates are not simply precursors of free triflic acid. Based on the kinetic and mechanistic evidence, the proposed catalytic pathway invokes hydroxyl and olefin activation by the electron-deficient Ln(3+) center, and intramolecular H(+) transfer, followed by alkoxide nucleophilic attack with ring closure.

Cationic Polymerization of Vinyl Monomers in Aqueous Media: From Monofunctional Oligomers to Long-Lived Polymer Chains

Polymer latexes are easily prepared on a multimillion ton scale in industry using free radical initiated emulsion and suspension polymerizations in water, a cheap, nonviscous, heat-controlling, and environmentally benign solvent. Until recently, researchers had done little investigation into ionic polymerization because even a small amount of water would easily deactivate the conventional catalysts used in these processes. In the last decade, however, cationic polymerization in aqueous media has emerged as a new and attractive method for controlling the polymerization reactions using mild experimental conditions. This Account reviews the current science of and future outlook for cationic polymerization of vinyl monomers in aqueous media. We particularly emphasize the design and evolution of catalytic systems and the precision synthesis of functional polymers. Early work to tailor the suspension and emulsion cationic polymerizations of reactive monomers such as p-methoxystyrene and vinyl ethers used long-chain strong acids, called INISURF for their dual roles as initiators and surfactants, and lanthanide triflates. These polymerization processes shared two main features: (i) all reactions (initiation, propagation, and termination) occurred at the particle interface; (ii) synthesized polymers have limits on their molecular weight, attributed to the "critical DP" effect, related to the entry of oligomers inside the particles as they become increasingly hydrophobic. The next generation of catalysts, named "Lewis acid-surfactant combined catalysts" (LASC), shifted the polymerization locus from the interface to the inside of the monomer droplets, allowing for the production of long polymer chains. Recently, catalytic systems based on boranes, (BF(3)OEt(2), B(C(6)F(5))(3), (C(6)F(4)-1,2-[B(C(6)F(5))(2)]), and (C(6)F(4)-1,2-[B(C(12)F(8))](2))), have shown great potential in controlling the cationic polymerization in "wet" solution, containing an excess of water relative to Lewis acid, or aqueous media of such industrially important monomers as styrene, cyclopentadiene, and even isobutylene.

Rare earth triflates/chlorotrimethylsilane induced activation of triethylamine as a latent acetaldehyde anion: a new synthesis of α,β-unsaturated aldehydes

A synthetic methodology for α,β-unsaturated aldehydes employing rare earth triflate is reported. Activated triethylamine reacts with aldehydes to form two carbon extended aldehydes, which is promoted by a catalytic amount of Yb, Sc, Y, and In(OTf) 3, in the presence of chlorotrimethylsilane. We investigated the conditions applicable to aromatic aldehydes as well as heterocyclic compounds as substrates. A deuterium labeling experiment supported our proposed reaction mechanism.

New thermosetting nanocomposites prepared from diglycidyl ether of bisphenol and γ-valerolactone initiated by rare earth triflate initiators

Mixtures of diglycidyl ether of bisphenol A (DGEBA) with γ-valerolactone (γ-VL) 2:1 (mol/mol) with different organically modified clays were cationically copolymerized in the presence of scandium, ytterbium or lanthanum triflates as initiators. The cure process was followed by calorimetry and rheological techniques. The differences in the gelation time on adding clays were studied by rheological measurements. These methods, in addition to FTIR studies of the cure process allowed selection of the best initiator and its concentration to achieve creation of the nanocomposite. The enhanced thermal stability of the nanocomposites was confirmed by thermogravimetric analysis (TGA). The intercalated morphology of the nanocomposites obtained was confirmed by transmission electron microscopy. The nanocomposites prepared showed a more plastic fracture surface than the unfilled material. Thermomechanical characteristics were also studied.

ChemInform Abstract: Aza‐Diels—Alder Reactions with Lanthanide Triflates: Syntheses of Quinoline and Phenanthridine Derivatives.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Effective and recoverable homogeneous catalysts for the transesterification of dimethyl carbonate with ethanol: Lanthanide triflates

The catalytic activities of metal triflates were tested for the transesterification of dimethyl carbonate (DMC) with ethanol. It was found that yttrium triflate was the most efficient homogeneous catalyst. When the transesterification reaction was catalyzed by yttrium triflate at 76–80°C, 7 h, ethanol to DMC in 6: 1 molar ratio, 0.35 mol % of catalyst based on DMC, the conversion of DMC was 89.2%, the selectivities of diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) were 85.1 and 13.6%, respectively. Yttrium triflate was reused 5 times for the transesterification without loss of its catalytic activity.

ChemInform Abstract: Efficient Intramolecular Hydroalkoxylation/Cyclization of Unactivated Alkenols Mediated by Lanthanide Triflate Ionic Liquids.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Aza-Diels–Alder Reactions with Lanthanide Triflates: Syntheses of Quinoline and Phenanthridine Derivatives

The aza-Diels–Alder reactions of cyclopentadiene and cyclo-1,3-hexadiene with various substituted N-arylimines in the presence of Yb/Sc triflates as catalyst in MeCN at room temperature gave quinoline and phenanthridine derivatives in moderate to high yields. Some of the cycloaddition reactions were carried out in ionic liquid.

Lanthanide Triflate Catalyzed Hetero-annulation Route to Tetrahydroquinolines

Lanthanide Triflate Catalyzed Hetero-annulation Route to Tetrahydroquinolines

Efficient Intramolecular Hydroalkoxylation/Cyclization of Unactivated Alkenols Mediated by Lanthanide Triflate Ionic Liquids

Lanthanide triflates, Ln(OTf)(3), serve as efficient catalysts for the intramolecular hydroalkoxylation (HO)/cyclization of primary/secondary and aliphatic/aromatic hydroxyalkenes in room temperature ionic liquids (RTILs). Cyclizations are effective in the formation of five- and six-membered oxygen heterocycles with Markovnikov-type selectivity. Reaction rates exhibit first-order dependence on [Ln(3+)] and [substrate].

Lanthanide (III) salt complexes: Arrayed acid‐base networks for enantioselective catalysis. The nitroaldol reaction upon aldehydes and trifluoromethylketones

Shelf stable, chiral-at-metal, D(3) symmetric, 3:1 complexes of lanthanide (III) triflate salts are easily available by complexation with binolam (3,3'-diethylaminomethyl-2,2'-dihydroxy-1,1'-dinaphthalene) 1 or binolamo (3,3'-diethylaminooxymethyl-2,2'-dihydroxy-1,1'-dinaphthalene) 2 ligands. The resulting compounds 3Ln and 4Ln are isostructural, as demonstrated by their spectroscopic data, and possess an arrayed acid-base LABABB network. Complexes are kinetically labile, and in solution undergo hydrolysis by water. The lanthanum complex derived from binolam, i.e., (Delta,S,S,S)- (binolam)(3).la(OTf)(3)3La was found to be the most active catalyst in promoting direct nitroaldol reactions upon aldehydes and trifluoromethyl ketones, thereby giving rise to secondary nitroalcohols and tertiary alpha-trifluoromethyl-beta-nitroalcohols, respectively, with high ee in both cases. Enantiomerically enriched tertiary nitroalcohols were easily reduced to the corresponding aminoalcohols having a quaternary asymmetric carbon without loss of enantiomeric purity.

A dream combination for catalysis: highly reactive and recyclable scandium(iii) triflate-catalyzed cyanosilylations of carbonyl compounds in an ionic liquid

The catalytic activity of lanthanide triflates, particularly scandium triflate, increased dramatically in [bmim][SbF6], allowing the cyanosilylation of a variety of aldehydes and ketones with a turnover frequency up to 48 000 mol h−1 and a total turnover number of 100 000.