A Direct Method for β-Selective Glycosylation with an N-Acetylglucosamine Donor Armed by a 4-O-TBDMS Protecting Group

Hidenori Tanaka; Yu Hamaya; Hiyoshizo Kotsuki

doi:10.3390/molecules22030429

A Direct Method for β-Selective Glycosylation with an N-Acetylglucosamine Donor Armed by a 4-O-TBDMS Protecting Group

Molecules. 2017 Mar 8;22(3):429. doi: 10.3390/molecules22030429.

Authors

Hidenori Tanaka¹, Yu Hamaya², Hiyoshizo Kotsuki³

Affiliations

¹ Oceanography Section, Science Research Center, Kochi University, Otsu, Nankoku-shi, Kochi 783-8502, Japan. htanaka@kochi-u.ac.jp.
² Laboratory of Natural Products Chemistry, Faculty of Science, Kochi University, Akebono-cho, Kochi-shi, Kochi 780-8520, Japan. a_paradise_country@yahoo.co.jp.
³ Laboratory of Natural Products Chemistry, Faculty of Science, Kochi University, Akebono-cho, Kochi-shi, Kochi 780-8520, Japan. kotsuki@kochi-u.ac.jp.

Abstract

A new direct method for β-selective glycosylation with an N-acetylglucosamine (GlcNAc) donor was developed. This substrate, which can be readily prepared from commercially available GlcNAc in two steps, contains a 4-O-tert-butyldimethylsilyl (TBDMS) protecting group as a key component. We found that this functionality could have a favorable effect on the reactivity of the GlcNAc donor. Glycosylation with the armed donor using primary alcohols in the presence of a catalytic amount of trimethylsilyl trifluoromethanesulfonate (TMSOTf) in 1,2-dichloroethane smoothly gave the desired coupling products in good yields with complete β-selectivity, while sterically hindered acceptors were less efficient.

Keywords: N-acetylglucosamine; O-TBDMS protecting group; remote protecting group effect; β-selective glycosylation.

MeSH terms

Acetylglucosamine / chemistry*
Glycosylation
Organic Chemistry Phenomena

Substances

Acetylglucosamine