Efficient Differentiation of the Hydroxyl Groups of 3,4-O-Isopropylidene-D-Galactopyranosides by Lipase Catalyzed Esterification and De - Esterification

• Published in: Journal of carbohydrate chemistry Vol. 16; no. 7; pp. 1001 - 1010
• Main Authors: Barili, Pier Luigi, Catelani, Giorgio, D'Andrea, Felicia, Mastrorilli, Ettore
• Format: Journal Article
• Language: English
• Published: NEW YORK Taylor & Francis Group 01.09.1997; Marcel Dekker Inc
• Subjects: Biochemistry & Molecular Biology; Chemistry; Chemistry, Organic; Life Sciences & Biomedicine; Physical Sciences; Science & Technology; DERIVATIVES; D-GALACTOSE; ACID
• ISSN: 0732-8303; 1532-2327
• DOI: 10.1080/07328309708005733

The Pseudomonas sp. (LPS) promoted acyl transfer from vinyl acetate to selected 3,4-O-isopropylidene-D-galactopyranosides takes place in a completely selective manner giving in high yield the corresponding 6-O-acetates. The acetylation rate is strongly dependent on the type and the orientation of the aglycon, varying from a maximum of reactivity for the 1-deoxy derivative, 1,5-anhydro-3,4-O-isopropylidene-D-galactitol (1d), to a minimum for β configurated alkyl glycosides and showing a complete loss of reactivity for 3′,4′:2,3:5,6-tri-O-isopropylidenelactose dimethyl acetal (1e). The latter compound is, however, selectively 6′-O-esterified in good yield by lipase from Candida Antarctica and vinyl acetate. Also the course of the enzymatic hydrolysis of 2,6-di-O-acetyl-3,4-O-isopropylidene-D-galactopyranosides 2 is dependent on the type of the aglycon, both for the reaction rate and the selectivity. The 2-O-acetates 4 are selectively obtained in good yields with porcine pancreatic lipase (PPL) promoted hydrolysis in the case of β and α-methyl, and 1-deoxy derivatives (2a, 2b and 2d), while for β-benzyl (2c) and lactose (2e) analogues satisfactory results are obtained with lipase from Mucor miehei (IM20). Dedicated to the memory of Professor Giuseppe Bellucci