Minireview Recent advances in the glycosylation of sphingosines and ceramides Jose ´ Antonio Morales-Serna, Omar Boutureira, Yolanda Dı ´az, * M. Isabel Matheu * and Sergio Castillo ´n * Departament de Quı ´mica Analı ´tica i Quı ´mica Orga ` nica, Facultat de Quı ´mica, Universitat Rovira i Virgili, C/Marcelı ´ Domingo s/n, 43005 Tarragona, Spain Received 13 February 2007; received in revised form 27 March 2007; accepted 31 March 2007 Available online 11 April 2007 Abstract—Glycosphingolipids (GSLs) are ubiquitous components of eukaryotic cell membranes. They are highly bioactive and are involved in many aspects of cell signalling like cell–cell interaction, cell–substratum interaction and cell–pathogen interaction. GSLs also are involved in the modulation of signal transduction, resulting in regulation of cell proliferation and differentiation. The bio- logical importance and complexity of these compounds afford many opportunities to prepare synthetic analogues for studies of their metabolism in intra- and intercellular processes. This review focuses on recent contributions in the synthesis of GSLs, highlighting improvements in glycosylation reactions leading to a and b glycosyl sphingosines and ceramides and related compounds. Literature from 2000 to the present is covered. The glycosylation reactions leading to the synthesis of GSLs are classified in function of the configuration of the created glycosidic bond (a or b) and of the acceptor used, either azido-sphingosine or ceramide. Ó 2007 Elsevier Ltd. All rights reserved. Keywords: Carbohydrate; Glycosphingolipids; Glycosylation; Ceramides; Sphingosine; Phytosphintgosine Contents 1. Introduction................................................................ 1595 2. Synthesis of a-glycosyl sphingosines and ceramides ................................... 1597 2.1. Glycosylation of azido-sphingosines ....................................... 1597 2.2. Glycosylation of ceramides.............................................. 1599 3. Synthesis of b–glycosyl sphingosines and ceramides .................................. 1602 3.1. Glycosylation of azido-sphingosine ........................................ 1602 3.2. Glycosylation of ceramides.............................................. 1604 3.3. Enzymatic procedures ................................................. 1605 3.4. Miscellaneous methods ................................................ 1606 4. Conclusions ................................................................ 1609 Acknowledgements .......................................................... 1611 References ................................................................. 1611 1. Introduction Biological membranes 1 are described as a ‘mosaic of lipid domains’ where glycosphingolipids (GSLs) are building blocks of the plasma membrane and where their hydrophilic portions are exposed towards the cell 0008-6215/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.carres.2007.03.028 * Corresponding authors. Tel.: +34 977 559556; fax: +34 977 558446 (S.C.); e-mail: sergio.castillon@urv.net Carbohydrate Research 342 (2007) 1595–1612