'Five at one stroke': proline and small peptides in the stereoselective de novo synthesis and enantiotopic functionalization of carbohydrates

Abstract

Asymmetric catalysis with the simple amino acid proline (so called 'enamine catalysis') arrested big attention in the last few years since the re-discovery of the Hajos-Parrish-Eder-Sauer-Wiechert reaction. After basic mechanistic studies, probing scope and limitations of the catalyst and the corresponding reactions, this concept has now emerged to a state where it is applied to the assembly of up to five stereogenic centers of carbohydrates, not really 'at one stroke', but in only two simple synthetic operations. Beyond, it is not only possible to build up complicated natural products elegantly, but also to address selectively the similar functional groups of carbohydrates by small peptidic catalysts. This short review covers the recent developments of organocatalysis in both fields, with special emphasis on the asymmetric assembly and selective derivatization of carbohydrates.