Acuminosylation of Tyrosol by a Commercial Diglycosidase

Abstract

A commercial glycosidase mixture obtained from Penicillium multicolor (Aromase H2) was found to comprise a specific diglycosidase activity, β-acuminosidase, alongside undetectable levels of β-apiosidase. The enzyme was tested in the transglycosylation of tyrosol using 4-nitrophenyl β-acuminoside as the diglycosyl donor. The reaction was not chemoselective, providing a mixture of Osmanthuside H and its counterpart regioisomer 4-(2-hydroxyethyl)phenyl β-acuminoside in 58% yield. Aromase H2 is therefore the first commercial β-acuminosidase which is also able to glycosylate phenolic acceptors.

Rutinosides-derived from Sarocladium strictum 6-O-α-rhamnosyl-β-glucosidase show enhanced anti-tumoral activity in pancreatic cancer cells

“…Synthesis of a series of glycosides has been reported using diglycosidases [ 23 , 26 , 29 ]. However, the addition of rutinose moiety to phenolic acceptors is a rare event; for a long time, it had been believed that glycosidases employing a retaining mechanism were unable to glycosylate phenolic phenolic OH.…”

“…However, the addition of rutinose moiety to phenolic acceptors is a rare event; for a long time, it had been believed that glycosidases employing a retaining mechanism were unable to glycosylate phenolic phenolic OH. Up to now, few fungal diglycosidases were able to transglycosylate aromatic alcohols and usually, yields of transglycosylation reaction were reduced by the increment of the bulkiness of the acceptor [ 23 , 26 , 29 ]. The transglycosylation products of S. strictum DMic 093557 αRβG with methanol and ethanol were not detected, while the highest yield of transglycosylation was reached with longer carbon chain alcohols such as isoamylalcohol.…”

“…Among the GHs (EC 3.2.1.x), diglycosidases with synthetic activities [ 21 – 23 ], represent a suitable class of enzyme to generate glycoconjugates aimed at improving the efficacy of known anti-cancer agents. These enzymes are found in microorganisms and plants; fungal extracellular diglycosidases are among the most commonly used to perform glycosylation reactions with relatively high yields [ 24 – 27 ].…”

Acremonium sp. diglycosidase-aid chemical diversification: valorization of industry by-products

“…This achievement was made possible due to the specificity of the enzyme towards the sugar donor hesperidin, acting in a complex mixture of polysaccharides. Comparatively, the enzymatic preparation derived from Penicillium multicolor Aromase H2, the only commercially available diglycosidase, was successfully utilized for synthesizing diglycosylate tyrosol (Haluz et al 2023 ). This synthesis was possible because the mixture comprises a specific diglycosidase activity, β-acuminosidase, while having undetectable levels of β-apiosidase.…”

Robinobiosylation of tyrosol by seed meal from Rhamnus cathartica.

“…Contrary to the mentioned glycosylations with plant materials, the reaction catalyzed by seeds of R. cathartica was not chemoselective and provided in two separate reactions mixtures of isomers of tyrosol β-robinobioside 4a and 4b in ratios 5:1 and 8:1. The b-anomeric con guration for the galactopyranose ( The low ability to distinguish between the primary and phenolic hydroxyls of aglycon is more typical for microbial glycosidases (Bassanini et al 2017;Haluz et al 2023) and represents a complication in hydroxylation of tyrosol. We were not able to separate 4a and 4b each from other by standard column chromatography.…”