Steps Forward toward the Substitution of Conventional Solvents in the Heck–Mizoroki Coupling Reaction: Glycerol-Derived Ethers and Deep Eutectic Solvents as Reaction Media

Abstract

Glycerol-derived ethers and their eutectic mixtures with two renewable ammonium salts (ChCl and N00Cl) are effectively used as new green solvents for the immobilization of PVP-Palladium nanoparticles. Those air-stable, selective and recoverable catalytic systems are applied in the benchmark Heck-Mizoroki coupling reaction between iodobenzene and n-butyl acrylate in order to evaluate the influence of the different solvation properties of the solvent on the reaction results.The HBD ability (α acidity) of the solvent seems to play a crucial role in the reaction selectivity.

Lipids as versatile solvents for chemical synthesis

“…Exceptional performance of vegetable oils and related lipids as solvents was further confirmed for a number of other important Pd-catalyzed transformations, including the Hiyama, 18,19 Stille, 20,21 Sonogashira 22,23 and Heck 24,25 crosscoupling reactions.…”

“…27 1 H, 13 C and 19 F NMR spectra of rapeseed oil before and after the control experiments were identical. The Heck crosscoupling reaction is known to be quite sensitive to steric hindrance (Scheme 4, 11i,j), 24,25 which can be one of the reasons for the efficiency of vegetable oils and related systems as solvents.…”

Recent Advances in the Synthesis of Inorganic Materials Using Environmentally Friendly Media

“…Furthermore, ChCl:EG was used as a carrier and disperser for SiO 2 @Fe 3 O 4 (silica-coated magnetite) ferrofluids selective for Meloxicam [ 103 ], to electrodeposit Ni-Al nanocomposite coatings from NiCl 2 and aluminum dispersions [ 104 ], to synthesize platinum hollow-opened structures with enhanced performance in the electro-chemical oxidation of methanol [ 105 ], and as a solvent for assembling Ag nanoparticles onto copper substrates [ 106 ]. Glyceline was employed in the solvothermal preparation of functionalized metal-organic framework (MOF) nanoparticles containing zirconium [ 107 ], to immobilize Pd nanoparticles [ 108 ], and to deposit ZnO in situ on graphene sheets [ 109 ]. However, the real novelty of the last period consisted, as stated above, in the very large increase in the use of many new and alternative mixtures, often including biomolecules of natural origin.…”

Green Synthesis of Pd Nanoparticles for Sustainable and Environmentally Benign Processes

“…Very recently, Pires and co-workers designed glycerol-based solvents such as glycerol ethers and glycerol-based deep eutectic solvents (DES) for the immobilization and stabilization of Pd nanoparticles in liquid phases (PdNPs/solvent) and as a reaction media for catalytic application [176,177]. DES were obtained by mixing a glycerol-derived solvent with a bio-ammonium salt such as choline chloride or N,N,N-triethyl-2,3-dihydroxypropan-1-aminium chloride.…”

“…For the immobilization the Pd-NPs, two strategies have been used. The first involves contacting a dispersion of the Pd nanoparticles on poly-N-vinylpyrrolidone (PVP/PdNPs), prepared previously using EtOH as the reducing agent and PVP as the stabilizer, with the glycerol ethers or DES [176]. The dispersion of PdNPs in a glycerol-based solvent avoided a palladium agglomeration, allowing for the creation of a homogeneous PVP-Pd-NPs/solvent system which was tested using the Heck coupling reaction.…”