Solvent-Free Approaches in Carbohydrate Synthetic Chemistry: Role of Catalysis in Reactivity and Selectivity

Owing to their abundance in biomass and availability at a low cost, carbohydrates are very useful precursors for products of interest in a broad range of scientific applications. For example, they can be either converted into basic chemicals or used as chiral precursors for the synthesis of potentially bioactive molecules, even including nonsaccharide targets; in addition, there is also a broad interest toward the potential of synthetic sugar-containing structures in the field of functional materials. Synthetic elaboration of carbohydrates, in both the selective modification of functional groups and the assembly of oligomeric structures, is not trivial and often entails experimentally demanding approaches practiced by specialized groups. Over the last years, a large number of solvent-free synthetic methods have appeared in the literature, often being endowed with several advantages such as greenness, experimental simplicity, and a larger scope than analogous reactions in solution. Most of these methods are catalytically promoted, and the catalyst often plays a key role in the selectivity associated with the process. This review aims to describe the significant recent contributions in the solvent-free synthetic chemistry of carbohydrates, devoting a special critical focus on both the mechanistic role of the catalysts employed and the differences evidenced so far with corresponding methods in solution

Towards the semi-synthesis of phosphorylated mimics of glycosaminoglycans: Screening of methods for the regioselective phosphorylation of chondroitin

Glycosaminoglycan (GAG) mimics carrying phosphate rather than sulfate anionic groups have been poorly investigated, in spite of their interesting perspectives. While some GAG-mimicking phosphorylated polymers have been reported, to the best of our knowledge no phosphorylated polysaccharides having the same backbone of natural sulfated GAGs have been accessed yet. To fill this gap, in this work two standard phosphorylation protocols and two recently reported procedures have been screened on a set of polysaccharide species composed by microbial sourced chondroitin and three partially protected, semi-synthetic derivatives thereof. A detailed structural characterization by 1H, 13C and 31P NMR spectroscopy revealed the higher versatility of the innovative, biomimetic reaction employing monopotassium salt of phosphoenolpyruvate (PEP–K) with respect to standard phosphorylating agents (phosphoric acid or phosphorus oxychloride). Indeed, PEP-K and H3PO4 gave similar results in the regioselective phosphorylation of the primary hydroxyls of unprotected chondroitin, while only the former reacted on partially protected chondroitin derivatives in a controlled, regioselective fashion, affording chondroitin phosphate (CP) polysaccharides with different derivatization patterns. The reported results represent the first, key steps towards the systematic semi-synthesis of phosphorylated GAGs as a new class of GAG mimics and to the evaluation of their biological activities in comparison with native sulfated GAGs

Resonating bipolarons

Electrons coupled to local lattice deformations end up in selftrapped localized molecular states involving their binding into bipolarons when the coupling is stronger than a certain critical value. Below that value they exist as essentially itinerant electrons. We propose that the abrupt crossover between the two regimes can be described by resonant pairing similar to the Feshbach resonance in binary atomic collision processes. Given the intrinsically local nature of the exchange of pairs of itinerant electrons and localized bipolarons, we demonstrate the occurrence of such a resonance on a finite-size cluster made out of metallic atoms surrounding a polaronic ligand center.Comment: 7 pages, 4 figures, to be published in Europhysics Letter

Assemblage of oligosaccharides via one-pot multiglycosidations

conferenza plenaria su invito personalmente presentata, ABSTRACT LP-