Thiazolium salts as catalysts for etherification reaction

ChemInform Abstract: Palladium Supported on Cross-Linked Imidazolium Network on Silica as Highly Sustainable Catalysts for the Suzuki Reaction under Flow Conditions.

3-Mercaptopropyl-modified silica-supported bis-imidazolium Pd-catalysts are developed and successfully utilized for Suzuki reactions.

Palladium Supported on Cross-Linked Imidazolium Network on Silica as Highly Sustainable Catalysts for the Suzuki Reaction under Flow Conditions

Highly cross-linked imidazolium-based materials, obtained by radical oligomerization of bis-vinylimidazolium salts in the presence of 3-mercaptopropyl-modified silica gel, were used as supports for palladium catalysts. Thanks to the high imidazolium loading these materials were able to support a high amount of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer-Emmett-Teller technique, X-ray photoelectron spectroscopy, and transmission electron microscopy). The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds in high yields working with only 0.1 mol% of …

Thiazolium-based catalysts for the etherification reaction of benzylic alcohols under solvent-free condition

Thiazolium and imidazolium hybrid materials were prepared by radical reactions between a mercaptopropyl-modified SBA-15 mesoporous silica and bis-vinylthiazolium or bis-vinylimidazolium dibromide salts. These hybrid materials were characterized by several techniques and were employed in the etherification reaction of 1-phenylethanol. Solvent-free conditions at 160C under different gas phases (oxygen, air, nitrogen and argon) were used. The thiazolium-based material displayed excellent performances. Further studies were carried out using unsupported thiazolium salts, with or without a methyl group at the C-2 position of the thiazolium moiety. These studies allowed us to propose a reaction me…

Thiazolium-­‐based catalysts for the etherification of benzylic alcohols under solvent-­free conditions

In this work, thiazolium and imidazolium hybrid materials (SBA-15-Thia and SBA-15-Imi) were prepared by grafting the bis-vinylthiazolium or imidazolium salts onto thiol functionalized SBA-15 mesostructured silica. The catalytic activity was tested for the etherification of 1-phenylethanol, in heterogeneous conditions. The reactions were performed under different gas phases and reaction times. The SBA-15-Thia displayed an excellent catalytic performance, also with others benzyl alcohols. This material was successfully used in seven consecutive runs. Further studies were carried out in homogenous conditions. The results obtained allow proving that oxygen play an active role in the reaction pr…

Imidazolium functionalized carbon nanotubes for the synthesis of cyclic carbonates: reducing the gap between homogeneous and heterogeneous catalysis

Single walled carbon nanotubes (SWCNTs) were functionalized with imidazolium salts bearing vinyl functionalities. An extremely high loading of active species was achieved through a straightforward one-pot procedure involving self-assembly of the imidazolium moieties followed by radical initiated polymerization of the double bonds. The materials were extensively characterized by transmission electron microscopy, Raman spectroscopy, nitrogen physisorption and combustion chemical analysis. The imidazolium functionalized SWCNTs displayed excellent catalytic activity for the reaction of CO2 and epoxides to produce cyclic carbonates as demonstrated by the excellent turnover numbers (TON). Moreove…

ORGANIC-INORGANIC HYBRID CATALYSTS BASED ON IMIDAZOLIUM AND THIAZOLIUM SALTS

In the last years, great attention was focused on immobilized ionic liquids for their application in the field of catalysis. The main challenge is represented by the possibility of combining the benefits of the ionic liquids to that of the supports. In order to achieve this ambitious objective both the choice of the support and the functionalization strategy are of fundamental importance. In this context, one of the aims of this doctoral project was to develop novel catalysts based on covalently mono- or multilayer imidazolium or thiazolium networks onto a high ordered mesoporous silica or carbon nanotubes materials. The second goal of this PhD thesis was to design novel imidazolium based c…

ChemInform Abstract: Sequential Suzuki/Asymmetric Aldol and Suzuki/Knoevenagel Reactions under Aqueous Conditions.

Here we describe for the first time a sequential Suzuki/asymmetric aldol reaction. Such sequential approach was achieved through the combined use of an ionic liquid supported palladium catalyst and the organocatalyst trans-4-(2,2-diphenylacetoxy)proline. Suzuki and asymmetric aldol reactions were performed under aqueous conditions. The use of a palladium catalyst under basic conditions allowed also the first example of sequential Suzuki/Knoevenagel reaction. Reactions were carried out under aqueous conditions and products were isolated in good to high yields and, in the case of the Suzuki/aldol reaction, with diastereoselectivities up to 91:9 and enantioselectivities up to at least 99 %.

Sustainable Approach to Waste-Minimized Sonogashira Cross-Coupling Reaction Based on Recoverable/Reusable Heterogeneous Catalytic/Base System and Acetonitrile Azeotrope

In this contribution, we present a chemically efficient and sustainable protocol for the palladium-catalyzed copper-free Sonogashira cross-coupling reaction, based on the use of a heterogeneous catalytic system. This consists in the combination of a palladium catalyst on highly cross-linked thiazolidine network on silica and a polystyrene-supported base. The solid catalyst/base system acts as a palladium scavenger avoiding leaching of the metal and consequent product contamination. The reaction can be conducted in safe and easily recoverable acetonitrile/water azeotrope as reaction medium. This proved to be an efficient greener alternative to the classic toxic aprotic media commonly used in…

Cross-Linked Thiazolidine Network as Support for Palladium: A New Catalyst for Suzuki and Heck Reactions

A thiazolidine-based material was used for the first time as support for palladium. The support was prepared by starting from a highly cross-linked thiazolium-based material, obtained by radical oligomerization of a bisvinylthiazolium dibromide salt in the presence of 3-mercaptopropyl-modified silica SBA-15. Palladium was immobilized by treatment with tetrachloropalladate salt. Reduction with sodium borohydride afforded a thiazolidine-based material that acted as ligands for the Pd species. The thiazolidine-based palladium catalyst was fully characterized and, working in only 0.1 mol% amount, displayed good activity in the Suzuki-Miyaura and in the Heck reactions. Several biphenyl and alken…

Sequential Suzuki/Asymmetric Aldol and Suzuki/Knoevenagel Reactions Under Aqueous Conditions

Here we describe for the first time a sequential Suzuki/asymmetric aldol reaction. Such sequential approach was achieved through the combined use of an ionic liquid supported palladium catalyst and the organocatalyst trans-4-(2,2-diphenylacetoxy)proline. Suzuki and asymmetric aldol reactions were performed under aqueous conditions. The use of a palladium catalyst under basic conditions allowed also the first example of sequential Suzuki/Knoevenagel reaction. Reactions were carried out under aqueous conditions and products were isolated in good to high yields and, in the case of the Suzuki/aldol reaction, with diastereoselectivities up to 91:9 and enantioselectivities up to at least 99 %.

Novel Imidazolium Based Catalyst for the Chemical Fixation of Carbon Dioxide

A polyhedral oligomeric silsesquioxane-based catalyst for the efficient synthesis of cyclic carbonates

Polyhedral oligomeric silsesquioxane functionalized with imidazolium chloride peripheries (POSS-Imi) was successfully synthesized through a novel synthesis protocol. The solid was extensively characterized via1H NMR, 13C NMR and IR spectroscopy as well as combustion chemical analysis, mass spectrometry and transmission electron microscopy. Moreover, an in-depth investigation through 29Si NMR was performed. POSS-Imi was used for the first time as a catalyst for the conversion of CO2 and epoxides into cyclic carbonates with excellent results in terms of both yield and selectivity. The catalyst displayed improved catalytic performance with respect to unsupported 1-butyl-3-methylimidazolium chl…

Proximity Effect using a Nanocage Structure: Polyhedral Oligomeric Silsesquioxane-Imidazolium Tetrachloro- palladate Salt as a Precatalyst for the Suzuki-Miyaura Reaction in Water

A polyhedral oligomeric silsesquioxane-imidazolium tetrachloropalladate salt (POSS-Imi-PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane-imidazolium chloride salt (POSS-Imi-Cl) with PdCl2 and used as a pre-catalyst for the Suzuki-Miyaura reaction in water at 100 °C at a low loading (0.08-0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS-based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1-butyl-3-methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki-Miyaura reaction. This result is ascribed to a proximity effect of …

Polyhedral Oligomeric Silsesquioxane Based Catalyst for the Efficient Synthesis of Cyclic Carbonates

In this work, the synthesis of a novel imidazolium-based polyhedral oligomeric silsesquioxane (POSS-mim-Cl) material is presented. The new nanometer-size organosilica based compound was employed for chemical fixation of CO2 into epoxide under homogeneous conditions. The target reaction was represented by the obtention of cyclic carbonates starting from epoxides and CO2. Particularly, styrene oxide was chosen as reference substrate. In addition, different parameters (solvent, temperature, pressure of CO2, and mass of the catalyst) were modified to find the best condition for CO2 conversion. The catalyst POSS-mim-Cl displayed good catalytic performances, the best results being obtained at 40 …

Evidences of release and catch mechanism in the Heck reaction catalyzed by palladium immobilized on highly cross-linked-supported imidazolium salts

Abstract Palladium (10 wt%) on a highly cross-linked imidazolium-based material was used as catalyst in 0.1 mol% in the Heck reaction between several alkenes and aryl iodides. Products were obtained from good to high yields. Deeper investigations showed a release of Pd species in solution and their capture by the imidazolium-based support. When a sixfold amount of support was employed the re-captured Pd species (0.5–0.6 wt%) were not anymore catalytically active. This result represents a new interesting aspect of this work since the highly cross-linked imidazolium-based material can act also as Pd scavenger avoiding the release of the metal in solution. Important differences between Heck an…

Palladium supported on cross-linked imidazolium network on silica as highly sustainable catalysts for the Suzuki reaction