Interplay of Monosaccharide Configurations on the Deacetylation with Lipase-B

Overview

Journal J Org Chem

Publisher American Chemical Society

Date 2025 Jan 10

PMID 39791132

Authors

Kaarel Erik Hunt

Annette Miller

Kristin Liias

Tatsiana Jarg

Kadri Kriis

Tonis Kanger

Affiliations

Soon will be listed here.

Abstract

Configurational differences in monosaccharides determine the products and selectivity of the transesterification reaction with lipase-B (CAL-B). The β-anomers of peresterified pyranose monosaccharides tend to yield anomeric deprotection products, while the α-anomers preferentially react at the sixth or fourth position. CAL-B differentiates between enantiomers, either reacting more rapidly with d-enantiomers of monosaccharides or having a different selectivity based on the enantiomer. Pivaloylated and benzoylated saccharides are the limits of the CAL-B transesterification reaction, while lower boiling point alcohols such as MeOH and EtOH can replace -BuOH as the nucleophilic reagent. Finally, CAL-B can be successfully recycled in both long and short reaction time reactions.

References

Zangelmi E, Ronda L, Castagna C, Campanini B, Veiga-da-Cunha M, Van Schaftingen E . Off to a slow start: Analyzing lag phases and accelerating rates in steady-state enzyme kinetics. Anal Biochem. 2020; 593:113595. DOI: 10.1016/j.ab.2020.113595. View

Scopes R . The effect of temperature on enzymes used in diagnostics. Clin Chim Acta. 1995; 237(1-2):17-23. DOI: 10.1016/0009-8981(95)06060-q. View

Hunt K, Garcia-Sosa A, Shalima T, Maran U, Vilu R, Kanger T . Synthesis of 6'-galactosyllactose, a deviant human milk oligosaccharide, with the aid of lipase-B. Org Biomol Chem. 2022; 20(23):4724-4735. DOI: 10.1039/d2ob00550f. View

Govindarajan M . Protecting group migrations in carbohydrate chemistry. Carbohydr Res. 2020; 497:108151. DOI: 10.1016/j.carres.2020.108151. View

Bandara M, Stine K, Demchenko A . The chemical synthesis of human milk oligosaccharides: Lacto-N-neotetraose (Galβ1→4GlcNAcβ1→3Galβ1→4Glc). Carbohydr Res. 2019; 483:107743. PMC: 6717531. DOI: 10.1016/j.carres.2019.107743. View

Seeberger P . The logic of automated glycan assembly. Acc Chem Res. 2015; 48(5):1450-63. DOI: 10.1021/ar5004362. View

Brzozowski A, Derewenda U, Derewenda Z, Dodson G, Lawson D, Turkenburg J . A model for interfacial activation in lipases from the structure of a fungal lipase-inhibitor complex. Nature. 1991; 351(6326):491-4. DOI: 10.1038/351491a0. View

Lairson L, Henrissat B, Davies G, Withers S . Glycosyltransferases: structures, functions, and mechanisms. Annu Rev Biochem. 2008; 77:521-55. DOI: 10.1146/annurev.biochem.76.061005.092322. View

Dong H, Zhou Y, Pan X, Cui F, Liu W, Liu J . Stereoelectronic control in regioselective carbohydrate protection. J Org Chem. 2012; 77(3):1457-67. DOI: 10.1021/jo202336y. View

10.

Kulkarni S, Wang C, Sabbavarapu N, Podilapu A, Liao P, Hung S . "One-Pot" Protection, Glycosylation, and Protection-Glycosylation Strategies of Carbohydrates. Chem Rev. 2018; 118(17):8025-8104. DOI: 10.1021/acs.chemrev.8b00036. View

11.

Nielsen M, Pedersen C . Catalytic Glycosylations in Oligosaccharide Synthesis. Chem Rev. 2018; 118(17):8285-8358. DOI: 10.1021/acs.chemrev.8b00144. View

12.

Nicoletti G, Cipolatti E, Valerio A, Carbonera N, Soares N, Theilacker E . Evaluation of different methods for immobilization of Candida antarctica lipase B (CalB lipase) in polyurethane foam and its application in the production of geranyl propionate. Bioprocess Biosyst Eng. 2015; 38(9):1739-48. DOI: 10.1007/s00449-015-1415-6. View

13.

Uppenberg J, Ohrner N, Norin M, Hult K, Kleywegt G, Patkar S . Crystallographic and molecular-modeling studies of lipase B from Candida antarctica reveal a stereospecificity pocket for secondary alcohols. Biochemistry. 1995; 34(51):16838-51. DOI: 10.1021/bi00051a035. View

14.

Zieniuk B, Fabiszewska A, Bialecka-Florjanczyk E . Screening of solvents for favoring hydrolytic activity of Candida antarctica Lipase B. Bioprocess Biosyst Eng. 2019; 43(4):605-613. DOI: 10.1007/s00449-019-02252-0. View

15.

Powers J, Asgian J, Ekici O, James K . Irreversible inhibitors of serine, cysteine, and threonine proteases. Chem Rev. 2002; 102(12):4639-750. DOI: 10.1021/cr010182v. View

16.

Ghosh B, Kulkarni S . Advances in Protecting Groups for Oligosaccharide Synthesis. Chem Asian J. 2020; 15(4):450-462. DOI: 10.1002/asia.201901621. View