Acetyl Group Migration in Xylan and Glucan Model Compounds as Studied by Experimental and Computational Methods

It was recently demonstrated by us that acetyl groups in oligosaccharides can migrate not only within one saccharide unit but also between two different saccharide units. Kinetics of this phenomenon were previously investigated in both mannan model compounds and a naturally occurring polysaccharide. In addition to mannans, there are also several other naturally acetylated polysaccharides, such as xyloglucans and xylans. Both xyloglucans and xylans are some of the most common acetylated polysaccharides in nature, displaying important roles in the plant cells. Considering the various biological roles of natural polysaccharides, it could be hypothesized that the intramolecular migration of acetyl groups might also be associated with regulation of the biological activity of polysaccharides in nature. Consequently, a better understanding of the overall migration phenomenon across the glycosidic bonds could help to understand the potential role of such migrations in the context of the biological activity of polysaccharides. Here, we present a detailed investigation on acetyl group migration in the synthesized xylan and glucan trisaccharide model compounds by a combination of experimental and computational methods, showing that the migration between the saccharide units proceeds from a secondary hydroxyl group of one saccharide unit toward a primary hydroxyl group of the other unit

Mechanisms of Stereodirecting Participation and Ester Migration from Near and Far in Glycosylation and Related Reactions

This review is the counterpart of a 2018 Chemical Reviews article (Adero, P. O.; Amarasekara, H.; Wen, P.; Bohe, L.; Crich, D. Chem. Rev. 2018, 118, 8242-8284) that examined the mechanisms of chemical glycosylation in the absence of stereodirecting participation. Attention is now turned to a critical review of the evidence in support of stereodirecting participation in glycosylation reactions by esters from either the vicinal or more remote positions. As participation by esters is often accompanied by ester migration, the mechanism(s) of migration are also reviewed. Esters are central to the entire review, which accordingly opens with an overview of their structure and their influence on the conformations of six-membered rings. Next the structure and relative energetics of dioxacarbeniun ions are covered with emphasis on the influence of ring size. The existing kinetic evidence for participation is then presented followed by an overview of the various intermediates either isolated or characterized spectroscopically. The evidence supporting participation from remote or distal positions is critically examined, and alternative hypotheses for the stereodirecting effect of such esters are presented. The mechanisms of ester migration are first examined from the perspective of glycosylation reactions and then more broadly in the context of partially acylated polyols.Peer reviewe

Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods

Acyl group migration affects the synthesis, isolation, manipulation and purification of all acylated organic compounds containing free hydroxyl groups, in particular carbohydrates. While several isolated studies on the migration phenomenon in different buffers have been reported, comprehensive insights into the overall migration process in different monosaccharides under similar conditions have been lacking. Here, we have studied the acyl migration in different monosaccharides using five different acyl groups by a combination of experimental, kinetic and theoretical tools. The results show that the anomeric configuration in the monosaccharide has a major influence on the migration rate, together with the relative configurations of the other hydroxyl groups and the nature of the migrating acyl group. Full mechanistic model, based on computations, demonstrates that the acyl migration proceeds through an anionic stepwise mechanism with linear dependence on the OH-] and the pK(a) of the hydroxyl group toward which the acyl group is migrating

Kinetic Studies of Acetyl Group Migration between the Saccharide Units in an Oligomannoside Trisaccharide Model Compound and a Native Galactoglucomannan Polysaccharide

Acyl group migration is a fundamental phenomenon in carbohydrate chemistry, recently shown to take place also between two non-adjacent hydroxyl groups, across the glycosidic bond, in a beta-(1 -> 4)-linked mannan trisaccharide model compound. With the central mannoside unit containing acetyl groups at the O2 and O3 positions, the O2-acetyl was in the earlier study shown to migrate to O6 of the reducing end. Potential implications of the general acyl migration process on cell signaling events and plant growth in nature are intriguing open questions. In the present work, migration kinetics in this original trisaccharide model system were studied in more detail together with potential interactions of the model compound and the migration products with DC-SIGN lectin. Furthermore, we demonstrate here for the first time that similar migration may also take place in native polysaccharides, here represented by galactoglucomannan from Norway spruce.The authors acknowledge the European Research Council for financial support (ERC-2017-AdG, project number 788143-RECGLYCA NMR) and the Agencia Estatal de Investigacion (Spain) for project RTI2018-094751-B-C21 (to JJB

Novel Dextran-Supported Biological Probes Decorated with Disaccharide Entities for Investigating the Carbohydrate–Protein Interactions of Gal-3

The quest for novel natural-like biomolecular probes that can be used to gain information on biological recognition events is of topical interest to several scientific areas. In particular, the recognition of carbohydrates by proteins modulates a number of important biological processes. These molecular recognition events are, however, difficult to study by the use of naturally occurring oligosaccharides and polysaccharides owing to their intrinsic structural heterogeneity and to the many technical difficulties encountered during the isolation of sufficient quantities of pure material for detailed structural and biological studies. Therefore, the construction of homogenous biomolecular probes that can mimic both the biophysical properties of polysaccharide backbones and the properties of bioactive oligosaccharide fragments are highly sought after. Herein, synthetic methodology for the construction of well-defined bioconjugates consisting of biologically relevant disaccharide fragments grafted onto a dextran backbone is presented, and a preliminary NMR spectroscopy study of their interactions with galectin-3 as a model lectin is conducted.Peer reviewe

Study of the sterile conk of Inonotus obliquus using 13C CPMAS NMR and FTIR spectroscopies coupled with multivariate analysis

The sterile conk caused by the infection of the basidiomycete Inonotus obliquus (Chaga) is an important source of bioactive compounds. However, its structure and biochemistry are only generally understood. Solid state 13C NMR and FTIR spectroscopy have been utilized for the first time to investigate the sterile conk with non-invasive methods. The application of multivariate data analysis techniques and spectral distance algorithm to the obtained datasets showed clear distinction between the outer and inner layers of the sterile conk. Moreover, the sterile conk bark, compared to the inner layers, was spectroscopically more similar to wood tissues. The fungal tissue was proven to be concentrated below the bark. The similarity of the sterile conk inner layers to both decayed wood and hyphae of I. obliquus was shown by the multivariate data analysis of both spectra datasets. The spectroscopic data indicated lack of lignin degradation in the heart rot, except for demethoxylation, and a slight preference for hemicellulose degradation. Therefore, the results obtained suggest that the classification of I. obliquus as preferential lignin degrader (white-rot fungus) should be revised and clarified by further studies.</p

Acetyl group migration across the saccharide units in oligomannoside model compound

Acetylated oligosaccharides are common in nature. While they are involved in several biochemical and biological processes, the role of the acetyl groups and the complexity of their migration has largely gone unnoticed. In this work, by combination of organic synthesis, NMR spectroscopy and quantum chemical modeling, we show that acetyl group migration is a much more complex phenomenon than previously known. By use of synthetic oligomannoside model compounds, we demonstrate, for the first time, that the migration of acetyl groups in oligosaccharides and polysaccharides may not be limited to transfer within a single monosaccharide moiety, but may also involve migration over a glycosidic bond between two different saccharide units. The observed phenomenon is not only interesting from the chemical point of view, but it also raises new questions about the potential biological role of acylated carbohydrates in nature.Peer reviewe

Novel Dextran-Supported Biological Probes Decorated with Disaccharide Entities for Investigating the Carbohydrate–Protein Interactions of Gal-3

The quest for novel natural‐like biomolecular probes that can be used to gain information on biological recognition events is of topical interest to several scientific areas. In particular, the recognition of carbohydrates by proteins modulates a number of important biological processes. These molecular recognition events are, however, difficult to study by the use of naturally occurring oligosaccharides and polysaccharides owing to their intrinsic structural heterogeneity and to the many technical difficulties encountered during the isolation of sufficient quantities of pure material for detailed structural and biological studies. Therefore, the construction of homogenous biomolecular probes that can mimic both the biophysical properties of polysaccharide backbones and the properties of bioactive oligosaccharide fragments are highly sought after. Herein, synthetic methodology for the construction of well‐defined bioconjugates consisting of biologically relevant disaccharide fragments grafted onto a dextran backbone is presented, and a preliminary NMR spectroscopy study of their interactions with galectin‐3 as a model lectin is conducted.</p

Glycosylation of phenolic acceptors using benzoylated glycosyl trichloroacetimidate donors

Benzoylated rhamnosyl and lactosyl trichloacetimidate donors were used in glycosylation reactions with phenolic acceptors. Both reactions proceeded with high selectivity. A new access to phenolic glycosides, which are common in nature and possess significant biological properties, has thus been reported