Francesco MESSA - Academia.edu (original) (raw)

Papers by Francesco MESSA

Catalysts

Polymeric materials are widely used in every human endeavor (bottles, clothes, containers, toys, ... more Polymeric materials are widely used in every human endeavor (bottles, clothes, containers, toys, tools, etc.) due to their unique properties of chemical and mechanical resistance. They are, however, almost non-biodegradable, and their chemical recycling into monomers is difficult and costly, thereby allowing their accumulation into the environment. This review highlights recent advances in the use of deep eutectic solvents (DESs) as catalysts and/or green solvents in plastics degradation, with the aim of designing greener processes for polymers’ chemical recycling, by reusing their monomers. These greener processes, in combination with other catalytic approaches, are aimed at introducing plastics as feedstock into the synthesis of other materials, according to the circular economy principles.

Organic & Biomolecular Chemistry

A gas-free alkoxycarbonylation of aryl iodides was performed in MePh3PBr/ethylene glycol DES by u... more A gas-free alkoxycarbonylation of aryl iodides was performed in MePh3PBr/ethylene glycol DES by using Mo(CO)6 as a safe source of CO. The reaction occurred under mild reaction conditions (80 °C) and with a low catalyst loading (0.5 mol%).

Journal of Archaeological Science: Reports

European Journal of Organic Chemistry

Molbank

A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), h... more A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), has been synthesized using a green approach. The reaction was conducted in a ChCl (cholinium chloride)/urea eutectic mixture, which is a nature-inspired and environmentally friendly reaction medium. The proposed reaction mechanism involves the preliminary regioselective alkylation of the Nsp2 of guanidine (2), followed by an intramolecular condensation between the carbonyl moiety and the secondary N′sp3. Finally, a tautomerization/aromatization step furnished the final product (3). Notably, 2-amino imidazole (3) could be isolated in high yield (91%), just by filtration from the DES/water mixture and subsequent crystallization; the remaining ChCl/urea could be recycled, after water removal, for four consecutive reactions without any significant drop in the (3) yield. The product has been fully characterized by 1H, 13C, 2D 1H-13C HSQC, and 2D 1H-13C HMBC NMR; FT-IR spectroscopy; and EI-MS s...

Molecules

The synthesis of heterocycles is a fundamental area of organic chemistry that offers enormous pot... more The synthesis of heterocycles is a fundamental area of organic chemistry that offers enormous potential for the discovery of new products with important applications in our daily life such as pharmaceuticals, agrochemicals, flavors, dyes, and, more generally, engineered materials with innovative properties. As heterocyclic compounds find application across multiple industries and are prepared in very large quantities, the development of sustainable approaches for their synthesis has become a crucial objective for contemporary green chemistry committed to reducing the environmental impact of chemical processes. In this context, the present review focuses on the recent methodologies aimed at preparing N-, O- and S-heterocyclic compounds in Deep Eutectic Solvents, a new class of ionic solvents that are non-volatile, non-toxic, easy to prepare, easy to recycle, and can be obtained from renewable sources. Emphasis has been placed on those processes that prioritize the recycling of cataly...

Organic & Biomolecular Chemistry

A chemo- and stereoselective Pd-catalysed semi-reduction of alkynes to (Z)-alkenes has been perfo... more A chemo- and stereoselective Pd-catalysed semi-reduction of alkynes to (Z)-alkenes has been performed in a phosphonium-based DES by using the in situ generation of H2 from Al/H2O. The antitumor agent combretastatin A4 has been also synthesized.

European Journal of Organic Chemistry

Molbank

The synthesis of a novel uracil derivative, 3-cyclohexyl-6-phenyl-1-(p-tolyl)pyrimidine-2,4(1H,3H... more The synthesis of a novel uracil derivative, 3-cyclohexyl-6-phenyl-1-(p-tolyl)pyrimidine-2,4(1H,3H)-dione (4), is reported via a four-component reaction involving an α-chloroketone (1), an aliphatic isocyanate (2), a primary aromatic amine (3) and carbon monoxide. The proposed reaction mechanism involves a Pd-catalyzed carbonylation of 2-chloro-1-phenylethan-1-one (1), leading to a β-ketoacylpalladium key intermediate, and, at the same time, in situ formation of non-symmetrical urea deriving from cyclohexyl isocyanate (2) and p-toluidine (3). After a chemo-selective acylation of the non-symmetrical urea and the subsequent cyclization of the acylated intermediate, 3-cyclohexyl-6-phenyl-1-(p-tolyl)pyrimidine-2,4(1H,3H)-dione (4) is formed. Uracil derivative 4 was isolated in good yield (73%) and fully characterized by 1H, 13C, 2D 1H-13C HSQC and 2D 1H-13C HMBC NMR, FT-IR spectroscopy and GC-MS spectrometry.

Advanced Synthesis & Catalysis, 2008

The coupling of primary and secondary unactivated alkyl bromides with alkyl-Grignard reagents was... more The coupling of primary and secondary unactivated alkyl bromides with alkyl-Grignard reagents was performed in good yields under mild conditions by using a new catalytic system: consisting of cobalt chloride and tetramethylethylenedi-A C H T U N G T R E N N U N G amine (CoCl 2 •2 LiI, 4 TMEDA). The reaction is very chemoselective since ketone, ester and nitrile functions are tolerated.

Journal of Polymers and the Environment

European Journal of Organic Chemistry

Green Chemistry

The in situ generation of H2 from aluminum powder and water/KOH enabled a general hydrogenation m... more The in situ generation of H2 from aluminum powder and water/KOH enabled a general hydrogenation method in cholinium chloride/glycerol deep eutectic solvent under Pd/C catalysis.

ChemCatChem, 2020

The commercially available and cheap Pd/C was found to promote Sonogashira couplings in the envir... more 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.

Journal of Heterocyclic Chemistry, 2020

A green synthesis of benzoxazines, based upon reaction of cardanol with formaldehyde and primary ... more A green synthesis of benzoxazines, based upon reaction of cardanol with formaldehyde and primary amines, is achieved in high yields using choline chloride-urea mixture as deep eutectic solvent. Then, it is demonstrated how the cardanol-based benxoxazines can be employed as only component for the preparation of a nanovesicular systems.

Chemical communications (Cambridge, England), Jan 17, 2018

A palladium-catalysed aminocarbonylation of (hetero)aryl iodides has, for the first time, been ac... more A palladium-catalysed aminocarbonylation of (hetero)aryl iodides has, for the first time, been accomplished in deep eutectic solvents as environmentally benign and recyclable media, under mild conditions. The reactions proceeded with a good substrate scope, and a variety of amides have been synthesized in yields up to 98%.

Tetrahedron, 2017

A novel and green synthesis of 2-pyrazinones in deep eutectic solvents (DESs) is described. Treat... more A novel and green synthesis of 2-pyrazinones in deep eutectic solvents (DESs) is described. Treatment of aromatic α-chloro oximes with aliphatic amines at 110 °C in choline chloride based DESs resulted in a straightforward and efficient assembly of 1,3,5-trisubstituted-2(1H)pyrazinones. The protocol, featuring mild reaction conditions and avoiding common volatile organic solvents, affords a safe and sustainable approach to original peptidomimetic scaffolds.

European Journal of Organic Chemistry, 2019

A Deep Eutectic Solvent like choline chloride/glycerol (1:2 mol mol-1) proved to be an effective,... more A Deep Eutectic Solvent like choline chloride/glycerol (1:2 mol mol-1) proved to be an effective, sustainable reaction medium to easily synthesize both phenacyl azides and symmetrical 2,5diarylpyrazines of interest in pharmacology and in coordination chemistry. Notable features of our report include: (i) nucleophilic substitution reactions of α-halo carbonyl compounds to the corresponding phenacyl azides compatible with the eutectic mixture, (ii) the reduction of phenacyl azides to α-amino carbonyl compounds, which undergo spontaneous dimerisation/cyclisation/aromatisation in the same eutectic mixture to provide valuable pyrazines. Telescoped, one-pot, two-steps stoichiometric/catalytic processes have also been successfully developed to furnish 2,5-diarylpyrazines in up to 95% yield.

Catalysts

Polymeric materials are widely used in every human endeavor (bottles, clothes, containers, toys, ... more Polymeric materials are widely used in every human endeavor (bottles, clothes, containers, toys, tools, etc.) due to their unique properties of chemical and mechanical resistance. They are, however, almost non-biodegradable, and their chemical recycling into monomers is difficult and costly, thereby allowing their accumulation into the environment. This review highlights recent advances in the use of deep eutectic solvents (DESs) as catalysts and/or green solvents in plastics degradation, with the aim of designing greener processes for polymers’ chemical recycling, by reusing their monomers. These greener processes, in combination with other catalytic approaches, are aimed at introducing plastics as feedstock into the synthesis of other materials, according to the circular economy principles.

Organic & Biomolecular Chemistry

A gas-free alkoxycarbonylation of aryl iodides was performed in MePh3PBr/ethylene glycol DES by u... more A gas-free alkoxycarbonylation of aryl iodides was performed in MePh3PBr/ethylene glycol DES by using Mo(CO)6 as a safe source of CO. The reaction occurred under mild reaction conditions (80 °C) and with a low catalyst loading (0.5 mol%).

Journal of Archaeological Science: Reports

European Journal of Organic Chemistry

Molbank

A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), h... more A new 2-amino imidazole derivative, 5-(4-chlorophenyl)-N,1-di-o-tolyl-1H-imidazole-2-amine (3), has been synthesized using a green approach. The reaction was conducted in a ChCl (cholinium chloride)/urea eutectic mixture, which is a nature-inspired and environmentally friendly reaction medium. The proposed reaction mechanism involves the preliminary regioselective alkylation of the Nsp2 of guanidine (2), followed by an intramolecular condensation between the carbonyl moiety and the secondary N′sp3. Finally, a tautomerization/aromatization step furnished the final product (3). Notably, 2-amino imidazole (3) could be isolated in high yield (91%), just by filtration from the DES/water mixture and subsequent crystallization; the remaining ChCl/urea could be recycled, after water removal, for four consecutive reactions without any significant drop in the (3) yield. The product has been fully characterized by 1H, 13C, 2D 1H-13C HSQC, and 2D 1H-13C HMBC NMR; FT-IR spectroscopy; and EI-MS s...

Molecules

The synthesis of heterocycles is a fundamental area of organic chemistry that offers enormous pot... more The synthesis of heterocycles is a fundamental area of organic chemistry that offers enormous potential for the discovery of new products with important applications in our daily life such as pharmaceuticals, agrochemicals, flavors, dyes, and, more generally, engineered materials with innovative properties. As heterocyclic compounds find application across multiple industries and are prepared in very large quantities, the development of sustainable approaches for their synthesis has become a crucial objective for contemporary green chemistry committed to reducing the environmental impact of chemical processes. In this context, the present review focuses on the recent methodologies aimed at preparing N-, O- and S-heterocyclic compounds in Deep Eutectic Solvents, a new class of ionic solvents that are non-volatile, non-toxic, easy to prepare, easy to recycle, and can be obtained from renewable sources. Emphasis has been placed on those processes that prioritize the recycling of cataly...

Organic & Biomolecular Chemistry

A chemo- and stereoselective Pd-catalysed semi-reduction of alkynes to (Z)-alkenes has been perfo... more A chemo- and stereoselective Pd-catalysed semi-reduction of alkynes to (Z)-alkenes has been performed in a phosphonium-based DES by using the in situ generation of H2 from Al/H2O. The antitumor agent combretastatin A4 has been also synthesized.

European Journal of Organic Chemistry

Molbank

The synthesis of a novel uracil derivative, 3-cyclohexyl-6-phenyl-1-(p-tolyl)pyrimidine-2,4(1H,3H... more The synthesis of a novel uracil derivative, 3-cyclohexyl-6-phenyl-1-(p-tolyl)pyrimidine-2,4(1H,3H)-dione (4), is reported via a four-component reaction involving an α-chloroketone (1), an aliphatic isocyanate (2), a primary aromatic amine (3) and carbon monoxide. The proposed reaction mechanism involves a Pd-catalyzed carbonylation of 2-chloro-1-phenylethan-1-one (1), leading to a β-ketoacylpalladium key intermediate, and, at the same time, in situ formation of non-symmetrical urea deriving from cyclohexyl isocyanate (2) and p-toluidine (3). After a chemo-selective acylation of the non-symmetrical urea and the subsequent cyclization of the acylated intermediate, 3-cyclohexyl-6-phenyl-1-(p-tolyl)pyrimidine-2,4(1H,3H)-dione (4) is formed. Uracil derivative 4 was isolated in good yield (73%) and fully characterized by 1H, 13C, 2D 1H-13C HSQC and 2D 1H-13C HMBC NMR, FT-IR spectroscopy and GC-MS spectrometry.

Advanced Synthesis & Catalysis, 2008

The coupling of primary and secondary unactivated alkyl bromides with alkyl-Grignard reagents was... more The coupling of primary and secondary unactivated alkyl bromides with alkyl-Grignard reagents was performed in good yields under mild conditions by using a new catalytic system: consisting of cobalt chloride and tetramethylethylenedi-A C H T U N G T R E N N U N G amine (CoCl 2 •2 LiI, 4 TMEDA). The reaction is very chemoselective since ketone, ester and nitrile functions are tolerated.

Journal of Polymers and the Environment

European Journal of Organic Chemistry

Green Chemistry

The in situ generation of H2 from aluminum powder and water/KOH enabled a general hydrogenation m... more The in situ generation of H2 from aluminum powder and water/KOH enabled a general hydrogenation method in cholinium chloride/glycerol deep eutectic solvent under Pd/C catalysis.

ChemCatChem, 2020

The commercially available and cheap Pd/C was found to promote Sonogashira couplings in the envir... more 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.

Journal of Heterocyclic Chemistry, 2020

A green synthesis of benzoxazines, based upon reaction of cardanol with formaldehyde and primary ... more A green synthesis of benzoxazines, based upon reaction of cardanol with formaldehyde and primary amines, is achieved in high yields using choline chloride-urea mixture as deep eutectic solvent. Then, it is demonstrated how the cardanol-based benxoxazines can be employed as only component for the preparation of a nanovesicular systems.

Chemical communications (Cambridge, England), Jan 17, 2018

A palladium-catalysed aminocarbonylation of (hetero)aryl iodides has, for the first time, been ac... more A palladium-catalysed aminocarbonylation of (hetero)aryl iodides has, for the first time, been accomplished in deep eutectic solvents as environmentally benign and recyclable media, under mild conditions. The reactions proceeded with a good substrate scope, and a variety of amides have been synthesized in yields up to 98%.

Tetrahedron, 2017

A novel and green synthesis of 2-pyrazinones in deep eutectic solvents (DESs) is described. Treat... more A novel and green synthesis of 2-pyrazinones in deep eutectic solvents (DESs) is described. Treatment of aromatic α-chloro oximes with aliphatic amines at 110 °C in choline chloride based DESs resulted in a straightforward and efficient assembly of 1,3,5-trisubstituted-2(1H)pyrazinones. The protocol, featuring mild reaction conditions and avoiding common volatile organic solvents, affords a safe and sustainable approach to original peptidomimetic scaffolds.

European Journal of Organic Chemistry, 2019

A Deep Eutectic Solvent like choline chloride/glycerol (1:2 mol mol-1) proved to be an effective,... more A Deep Eutectic Solvent like choline chloride/glycerol (1:2 mol mol-1) proved to be an effective, sustainable reaction medium to easily synthesize both phenacyl azides and symmetrical 2,5diarylpyrazines of interest in pharmacology and in coordination chemistry. Notable features of our report include: (i) nucleophilic substitution reactions of α-halo carbonyl compounds to the corresponding phenacyl azides compatible with the eutectic mixture, (ii) the reduction of phenacyl azides to α-amino carbonyl compounds, which undergo spontaneous dimerisation/cyclisation/aromatisation in the same eutectic mixture to provide valuable pyrazines. Telescoped, one-pot, two-steps stoichiometric/catalytic processes have also been successfully developed to furnish 2,5-diarylpyrazines in up to 95% yield.