In this review, we summarize results obtained using a conceptionally new chemical synthesis of NDP-sugars based on cycloSaligenyl (cycloSal) nucleotides as starting material (cycloSal technique). The cycloSal technique not only leads to stereoisomerically defined NDP-sugars in high yield, but the same principle provides very efficient routes towards nucleoside di- and -triphosphates. Moreover, sugar-nucleotides such as CMP-Neu5Ac and dinucleoside polyphosphates are available. Thus, the method offers a nearly universal chemical access towards a large number of highly interesting bioconjugates and biomolecules. (C) 2009 Elsevier GmbH. All rights reserved.