Cyclopentyl methyl ether and 2-methyltetrahydrofuran, low impact ethereal solvents forming a positive azeotrope with water, were successfully employed as solvents in the synthesis of a variety of acetals carried out under Dean–Stark conditions in the presence of heterogeneous acidic catalysts. Under these conditions, ammonium salts, either as such or supported on SiO2, performed better or equally well than widely employed homogeneous and heterogeneous acidic catalysts such as p-toluenesulfonic acid, Amberlyst 15®, or Montmorillonite K10. Several examples highlight the advantage of tuning the relative acidities of ammonium salts by appropriately selecting the counterion. Within one of these examples, our protocol clearly outweighs the classic p-toluenesulfonic acid/toluene protocol in terms of chemoselectivity. Silica-supported catalysts were characterized by SEM, TEM, and FTIR spectroscopies, as well as by N2 physisorption. Such a characterization reveals an even distribution of ammonium salts on silica, thus confirming the formation of expected catalytic supports.
20 October 2021 in European Journal of Organic Chemistry
In this work, mild Lewis acids and low environmental impact solvents were investigated for Nenitzescu synthesis. Cyclopentyl methyl ether can be used at room temperature in substitution of halogenated solvents with zinc, iron and magnesium salts as homogeneous catalysts to give 5‐hydroxyindoles in fair to good yields. The reaction features a straightforward workup and excellent solvent recycle.
G‐quadruplexes (G4 s), as non‐canonical DNA structures, attract a great deal of research interest in the molecular biology as well as in the material science fields. The use of small molecules as ligands for G‐quadruplexes has emerged as a tool to regulate gene expression and telomeres maintenance. Meso‐tetrakis‐(N‐methyl‐4‐pyridyl) porphyrin (TMPyP4) was shown as one of the first ligands for G‐quadruplexes and it is still widely used. We report an investigation comprising molecular docking and dynamics, synthesis and multiple spectroscopic and spectrometric determinations on simple cationic porphyrins and their interaction with different DNA sequences. This study enabled the synthesis of tetracationic porphyrin derivatives that exhibited binding and stabilizing capacity against G‐quadruplex structures; the detailed characterization has shown that the presence of amide groups at the periphery improves selectivity for parallel G4 s binding over other structures. Taking into account the ease of synthesis, 5,10,15,20‐tetrakis‐(1‐acetamido‐4‐pyridyl) porphyrin bromide could be considered a better alternative to TMPyP4 in studies involving G4 binding.
Biting midges (Culicoides spp.) are important vectors of several insect borne arboviruses but are underrepresented in terms of availability of high-resolution genomic resources. We assembled and annotated complete mitochondrial genomes for two Culicoides species, namely C. brevitarsis and C. imicola which are proven vectors for Bluetongue Virus (BTV). We used both long read and short read sequencing technologies to assemble the circular genomes. The genome sizes are 17,100 bp and 17,031 bp, respectively, all comprising 37 genes, including 13 protein, 22 tRNA, two rRNA coding genes, and one non-coding AT rich control region. The gene organizations and orientations are comparable to other available Culicoides mitogenomes, except for a translocation of ND2 and six tRNA genes in both C. brevitarsis and C. imicola. Eleven protein-coding genes encode a full TAA stop codon, while two (ND5, COX3) are completed by mRNA polyadenylation. Phylogenetic analysis of the mitogenomes showed C. brevitarsis and C. imicola form a monophyletic group. The sequences of these mitogenomes contribute to a baseline of molecular tools for diagnostics and surveillance for use by World Organisation for Animal Health (WOAH) reference laboratories for monitoring vectors of emerging diseases.
Reaction of glycerol with aldehydes and ketones is a strategy widely studied in literature to valorize this bioproduct. A Brønsted or Lewis acid is normally used to activate the carbonyl function and various strategies adopted to drive the equilibrium to the products. In this study ammonium salts as catalysts, and removal of water by azeotropic distillation of cyclopentyl methyl ether, permit the conversion of glycerol into acetals obtained as mixture of dioxanes and dioxolanes determined by 1 H‐NMR. Under the optimized conditions, the products could be obtained in excellent yield without using excess of reactants and the solvent was recycled efficiently.
Aryl and heteroaryl iodides have been efficiently converted into the corresponding thioacetates in cyclopentyl methyl ether (CPME), a green solvent, under Cu catalysis. The chemoselectivity of the reaction is mainly controlled by electronic factors, enabling the conversion of both electron-rich and electron-deficient substrates into the corresponding thioacetates in good to excellent yields. The products can be easily deprotected to the corresponding thiolates to carry out additional synthetic transformations in situ. Surprisingly, despite CPME’s relatively low dielectric constant, the reaction rate significantly increased when conducted under microwave irradiation conditions. This synthetic methodology exhibits a remarkable tolerance to functional groups, mild reaction conditions, and a wide substrate scope, utilizing a safe and inexpensive CuI pre-catalyst in the green solvent CPME. A non-aqueous workup allowing for the complete recovery of both catalyst and solvent makes this approach an environmentally sustainable protocol for C(sp2) sulfur functionalization. Additionally, the reaction shows selective cross-coupling with iodides in competition with chlorides and bromides, allowing its use in multistep syntheses. To demonstrate the potential of this methodology, it was applied to the high-yield synthesis of a photochromic dithienylethene, where a selective synthesis had not been reported before.