Synthesis and Evaluation of Fluorinated Benzyl Ethers as Alternate Protecting Groups for Enhanced NMR Resolution in Oligosaccharide Synthesis

Oligosaccharides have been playing an important role in biological systems. Synthesis of oligosaccharides requires the protection from hydroxyl groups present in the corresponding monosaccharide units. The existing methods of protection have drawbacks, including formation of anomeric mixtures, change in hydrophilicity or lipophilicity and solubility of the products, participation of the protecting groups in the reactions of the core of monosaccharide units, problems associated with chemoselectivity, regioselectivity and overall stereochemical outcomes of reactions. Additionally, there has been a spectral overlap of these protecting groups with carbohydrate core, which yielded more complex spectra. Therefore, the identification and synthesis of suitable alternative protecting groups have received attention in the oligosaccharide synthesis. The objective of the present study was to synthesize various fluorinated benzyl ethers of methyl-α-D-mannopyronoside and to evaluate these ethers as the alternative protecting groups for enhancing NMR resolution in the oligosaccharide synthesis. Various fluorinated benzyl ethers of methyl-α-D-mannopyronoside were prepared through the reaction of methyl-α-D-mannopyronoside with various fluorinated benzyl bromides by using Williamson ether synthesis method. Spectral analysis of these fluorinated benzyl ethers showed that the peaks of methylene carbons shifted to a value of 10-20 parts per million (ppm) to a high field region in the 13C NMR, compared to the non-fluorinated benzyl ether. As a result, the spectral complexity decreased and enhanced the spectral resolution. In this study, we concluded that fluorinated benzyl ethers could be a suitable alternative to the non-fluorinated benzyl ethers to protect the hydroxyl groups of monosaccharides in the synthesis of oligosaccharides.

Jet Colliding and Mixing Efficiency

Two experimental methods, the Nile Red dye extraction and the Williamson ether synthesis in biphasic conditions, were used to characterize the mixing performance of a new cheap impinging jet colliding mixer from Gjosa and to compare it to other commercial micromixers (Caterpillar CPMM-R300, T-mixer, LTF MR-MX and LTF MR-MS). The Nile Red method shows that the Caterpillar mixer is the best one. Excellent results are also achieved with two Gjosa mixers in series. These results are not reflected in the Williamson ether synthesis, where the best mixer is the Gjosa one.

Modelling and Environmental Aspects of Direct or Indirect Dimethyl Ether Synthesis Using Digestate as Feedstock

The conversion of waste and residues towards high added value products has receiving a growing attention, as a reliable strategy to improve sustainability of emergent processes. Anaerobic digestion converts organic waste into biogas and digestate. While biogas may be used for energetic purpose, digestate has limited uses and with a low profitability. In this paper, dimethyl ether (DME) is adopted as target product which may be produced from digestate-derived syngas. Process simulation is carried out for both direct and indirect synthesis of DME and environmental aspects are assessed.

An efficient bifunctional ionic liquid [BIL] as solvent and catalyst system for O-alkylation of phenols under solvent-free condition- An environmental benign approach

: Bifunctional ionic liquid [BIL] was found to be a highly effective catalyst for the ether synthesis without any inorganic base or solvent. By this protocol, different aryl substitutions were reacted with different phenol in good to excellent yields. The BIL is reusable without any loss in catalytic activity for nine consecutive cycles. Background: The Williamson reaction is a convenient renovation in fine chemical synthesis since the ethers are important in both bulk and fine industrial chemicals preparation and academic applications. Objective: The aim of this study is to highlight the use of BIL to synthesize mixed ethers using substituted phenols and to study the reusability in the next cycle. Method: The mixture of the phenol (1mmol), alcohol (1.2 mmol) and BIL ionic liquid (0.3 mol%) was added in to round-bottomed flask (100 mL) with continuous stirring for 1 hour. Results: The products obtained were phenol and substituted phenols containing withdrawing substituents in respectable yields. However, the reactions involving substituted phenols containing electron-donating groups often afford the corresponding products in low yields. Conclusion: BIL is found to be an effective catalyst in the etherification of various unsymmetrical ethers under mild conditions. Bifunctional ionic liquid as a solvent and catalyst will show real rewards by providing a ‘green’ method with the safer procedure, less reaction time periods, mild conditions, separation easy, and ionic liquid recycle.

Towards Dual-Metal Catalyzed Hydroalkoxylation of Alkynes

Poly (vinyl ethers) are compounds with great value in the coating industry due to exhibiting properties such as high viscosity, soft adhesiveness, resistance to saponification and solubility in water and organic solvents. However, the main challenge in this field is the synthesis of vinyl ether monomers that can be synthetized by methodologies such as vinyl transfer, reduction of vinyl phosphate ether, isomerization, hydrogenation of acetylenic ethers, elimination, addition of alcohols to alkyne species etc. Nevertheless, the most successful strategy to access to vinyl ether derivatives is the addition of alcohols to alkynes catalyzed by transition metals such as molybdenum, tungsten, ruthenium, palladium, platinum, gold, silver, iridium and rhodium, where gold-NHC catalysts have shown the best results in vinyl ether synthesis. Recently, the hydrophenoxylation reaction was found to proceed through a digold-assisted process where the species that determine the rate of the reaction are PhO-[Au(IPr)] and alkyne-[Au(IPr)]. Later, the improvement of the hydrophenoxylation reaction by using a mixed combination of Cu-NHC and Au-NHC catalysts was also reported. DFT studies confirmed a cost-effective method for the hydrophenoxylation reaction and located the rate-determining step, which turned out to be quite sensitive to the sterical hindrance due to the NHC ligands.