Xavier Marset

University of Alicante | UA · Organic Chemistry

Organic electrosynthesis has emerged as a unique platform for chemical manufacturing owing to not only the use of electricity as a green reagent, but especially, to its distinct reactivity. While conventional solvents are sought to remain inert and solely provide a liquid environment for the electrochemical process to occur, fluorinated alcohol sol...

Catalytic C−H functionalization has provided new opportunities to access novel organic molecules more sustainably and efficiently. However, these procedures typically rely on precious metals or complex organic catalysts as well as on hazardous solvents or reaction conditions. Herein, a pioneering methodology for direct C−C bond formation enabled by...

The Friedel–Crafts reaction is present in many fields of chemistry, being especially relevant in industrial applications, where it is one of the key methodologies to transform raw materials into functionalized aromatic products. During the last few years, the industry has been compelled to modify the conditions applied in its processes owing to the...

The regioselective functionalization of heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane (HCTD) under photocatalytic conditions is described. The protocols developed share an initial photo‐triggered hydrogen atom abstraction that regioselectively generates the necessary HCTD‐radical preferentially at position 1‐, they employ no excess of t...

In the presence of different nucleophilic Knoevenagel competitors, cyclic and acyclic ketones have been shown to undergo highly chemoselective aldol reactions with aldehydes. In doing so, the substrate breadth for this emerging methodology has been significantly broadened. The method is also no longer beholden to proline-based catalyst templates, e...

In the present study, for the first time environmentally friendly deep eutectic solvents (DESs) are used as reaction media to perform an efficient, simple and straightforward photocatalytic amide synthesis at room temperature using thioacids and amines. This method features mild conditions, a broad substrate scope, high yields (≤99%) under ambient...

This manuscript reports the synthesis and structure of an unprecedented sulfonium salt, 5‐(trifluorovinyl)dibenzothiophenium triflate, and its use as a versatile reagent for the introduction of the bioisosteric 1,1,2‐trifluoroethylene linker in drug‐like structures. The protocol developed consists of the reaction of this compound with alcohols and...

Our society is facing a tremendous challenge to become more sustainable in every sphere of life. Regarding the chemical industry, one of the most significant issues to be addressed is the use of volatile organic compounds (VOCs) as solvents because they are petrol-derived and most of them are toxic and flammable. Among the possible solutions, deep...

The Csp3-H activation of aliphatic amides is described for the first time in Deep Eutectic Solvents (DESs) without the need of Ag salts. The use of the eutectic mixtures improves...

A series of strong π‐acceptor polyfluorinated and dicationic chelating phosphines have been synthesized and evaluated in the Rh‐catalysed dimerization of norbornadiene (NBD) into its thermodynamically more stable dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane (HCTD). While dicationic ligands direct the dimerization towards HCTD,...

A selective and scalable two‐step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh‐catalyzed stepwise homo Diels–Alder cyclisation of NBD into its exo‐cis‐endo di...

Heptacyclotetradecane (HCTD) was synthesized through a two‐step process, which starts with the Rh‐catalyzed homo‐Diels Alder between two norbornadiene (nbd) units. Acidic treatment of the thus obtained intermediate affords the desired cage via sigmatropic rearrangement. The post‐synthetic functionalization of the HCTD scaffold is also described. A...

The easy synthesis of graphene oxide (GO)‐supported manganese dioxide (MnO2) nanoparticles as a stable heterogeneous nanocatalyst (MnO2@GO) is described. This catalyst was investigated in the synthesis of 1,2,4‐oxadiazoles from amidoximes and aldehydes via a cyclization and oxidation process. The nanocomposite was prepared and characterized using v...

This study describes a novel and catalyst‐free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non‐toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing the...

Deep eutectic solvents (DESs) were described at the beginning of this century as an alternative to ionic liquids (ILs) in green chemistry. Despite their obvious sustainable advantages as reaction media, there is still controversy about their potential toxicity. Most of the ecotoxicity assays done up to now involving DESs are based on antibiograms....

A strong σ-donor mesoionic carbene ligand has been synthesized and applied to four different palladium-catalyzed cross-coupling transformations, proving the catalyst/medium compatibility and the increased activity of this system over previous reports in Deep Eutectic Solvent medium. Some cross-coupling processes could be carried out at room tempera...

A sustainable and novel synthesis of sulfonamides using a copper-catalysed process starting from triarylbismuthines, Na2S2O5 and nitro compounds is described, introducing a new Deep Eutectic Solvent (DES) as reaction medium. The use of volatile organic compounds (VOCs) as solvents is avoided in the entire process. This one-pot synthetic method is e...

A NCN-pincer-Pd complex have been synthetized and applied to Hiyama-type cross-coupling reactions using neoteric solvents. This report constitutes a green approach to cross-coupling reactions since the reagents employed are stable and non-toxic. Also, the employed solvents (Deep Eutectic Solvents based on choline chloride or glycerol) are biodegrad...

A unique jigsaw catalytic system based on deep eutectic solvents and palladium nanoparticles, where C-S bonds are formed from aryl boronic acids and sodium metabisulfite, is introduced. The functionalization step is compatible with a broad spectrum of reagents such as nucleophiles, electrophiles or radical scavengers. This versatile approach allows...

Cationic pyridiniophosphine ligands have been synthetized in an attempt to develop a deep eutectic solvents (DESs) compatible catalytic systems. These ligands, in combination with PdCl2, have been successfully applied to different palladium-catalyzed cross coupling reactions, such as Suzuki-Miyaura, Sonogashira, or Heck couplings. While traditional...

Various tetrahydroisoquinoline derivatives are prepared by a cross-dehydrogenative coupling reaction using choline chloride/ethylene glycol (1:2) as a deep eutectic solvent (DES).

The synthesis of different tetrahydroisoquinolines using choline chloride:ethylene glycol as a deep eutectic solvent (DES) and copper(II) oxide impregnated on magnetite as a catalyst has been accomplished successfully. The copper catalyst amount is the lowest loading ever reported. The presence of DES showed to be essential since the reaction in th...