Chemoenzymatic Synthesis of New Aromatic Esters of Mono- and Oligosaccharides

Abstract

An efficient and convenient chemoenzymatic route for the synthesis of novel phenolic mono-, di- and oligosaccharide esters is described. Acetal derivatives of glucose, sucrose, lactose and inulin were obtained by chemical synthesis. The fully characterized pure sugar acetals were subjected to enzymatic esterification with 3-(4-hydroxyphenyl) propionic acid (HPPA) in the presence of Novozyme 435 lipase as a biocatalyst. The aromatic esters of alkyl glycosides and glucose acetal were obtained with good esterification yields, characterized by mass spectrometry (MALDI-TOF MS), infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (1H NMR, 13C NMR). The synthesis of aromatic esters of disaccharide acetals was successful only for the enzymatic esterification of sucrose acetal. The new chemoenzymatic route allowed the synthesis of novel aromatic esters of inulin as the inulin monoacetal monoester and diester and the inulin diacetal monoester with a polymerization degree of two, as well as the inulin monoacetal monoester with a degree of polymerization of three, were obtained by enzymatic acylation of inulin acetals with HPPA. These compounds could represent a new class of sugar ester surfactants with enhanced bioactivity, antioxidative and antimicrobial properties and with potential application in drug delivery systems.

Latest Trends in Lipase-Catalyzed Synthesis of Ester Carbohydrate Surfactants: From Key Parameters to Opportunities and Future Development

“…The term 'hybrid catalysis' is often used [141]. Buzatu et al synthesized acetal derivatives of glucose, sucrose, and lactose by chemical means and then performed enzymatic esterification using Novozym435 ® with 3(4-hydroxyphenyl)propionic acid [142]. Hybrid catalysis also makes it possible to get rid of the carbohydrate solubility problems.…”

“…Indeed, it is possible to chemically modify glucose to obtain a less polar derivative, and thus solubilize it. This will limit bioavailability issues in the subsequent steps [142]. Sangiorgo et al have thus derivatized glucose with 1-butanol using an Amberlyst 15 acid catalyst, and then conducted an esterification by Novozym435 ® with lauric acid [143].…”

The effects of protecting and acyl groups on the conformation of benzyl α-L-rhamnopyranosides: An in silico study

“…The presence of several secondary hydroxyl groups with almost similar reactivity imposes a barrier on selective esterification [13]. In this respect various methods were developed and employed successfully [14][15][16][17][18][19]. Among the SEs, synthetic rhamnopyranosides were reported to show promising activities like neuroprotective [20], antidepressant [21][22], anticarcinogenic [23], antimicrobial [24][25][26], and pharmacological properties [27] as well as in bioremediation of pollutants.…”

Self‐assembled trehalose amphiphiles as molecular gels: A unique formulation to wax‐free cosmetics

“…Sugar fatty acid esters (SFAEs) have been extensively used as surfactants, emulsifiers, stabilizers, and emollients in a variety of cosmetic products (Pérez et al, 2017). At the industrial level, SFAEs synthesis is carried out by chemical methods, involving severe conditions such as high temperature, use of hazardous chemicals, and generation of undesirable byproducts (Buzatu et al, 2020). However, chemical methods are not safe as they could leave traces of organic solvents.…”