On why benzylidene protecting groups are not effective for formylphenol glycosides
https://doi.org/10.21285/2227-2925-2019-9-2-212-221
Abstract
Benzylidene protecting groups are widely used in carbohydrate chemistry, as a rule, to protect the hydroxyl groups at O-4 and O-6 positions of the carbohydrate residue. With varying degrees of selectivity, 4,6-benzylidene protection allows introduction of other functional groups at O-2 and O-3 positions of sugars and is easily removed from the molecule under acidic conditions. We have previously proposed a scheme for obtaining acyl derivatives of natural glycoside salicin (glycoside of salicylic alcohol) from the intermediate glycoside helicin (glycoside of salicylic aldehyde). The aldehyde group can be reduced to alcohol during the final synthesis stages. Moreover, this group does not require additional protection during the modification of the carbohydrate residue, since it does not participate in acylation reactions, unlike the hydroxymethylene group of salicin. For the temporary protection of O-4 and O-6 hydroxyls of helicin, it was proposed to use a benzylidene protecting group. In this paper, we set out to study the reactivity of helicin in the reaction of 4,6-benzylidene formation, as well as to establish factors affecting such processes. Attempts were undertaken to introduce a benzylidene protecting group into a helicin molecule in two ways: using benzaldehyde dimethyl acetal, as well as using benzaldehyde and zinc chloride. In the former case, the conversion of the original glycoside was not observed, while the second reaction resulted in the product of an unidentified structure. Possible reactions occurring with the reagents applied were modelled using quantum-chemical calculations. It is found that the inability of benzaldehyde dimethyl acetal and benzaldehyde to react on 4,6 hydroxyls of glucose is explained by the competing reaction of the aldehyde group in the structure of helicin. Moreover, the catalysis with zinc chloride most likely produces a helicin dimer. Thus, it is found that benzylidene protection has certain limitations and cannot be applied in the case of glycosides containing aromatic aldehydes as the aglycone part.
Keywords
Supporting agencies: This work was financially supported by Russian fond of fundamental research project № 18-33-00365.
About the Authors
K. M. Faiskanova
Tomsk Polytechnic University
Russian Federation
Russian Federation
Master Student,
Tomsk
E. V. Stepanova
Tomsk Polytechnic University
Russian Federation
Russian Federation
Ph.D. (Chemistry), Senior Lecturer, Research School of Chemistry & Applied Biomedical Sciences,
Tomsk
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For citations:
Faiskanova K.M., Stepanova E.V. On why benzylidene protecting groups are not effective for formylphenol glycosides. Proceedings of Universities. Applied Chemistry and Biotechnology. 2019;9(2):212-221. (In Russ.) https://doi.org/10.21285/2227-2925-2019-9-2-212-221
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