Enzymatic Synthesis of ß‐L‐Fucose‐1‐phosphate and GDP‐fucose

Fucose is an important component of complex heterooligosaccharides. Here we describe the preparative enzymatic synthesis of ß‐ L ‐fucose‐1‐phosphate as well as its enzymatic conversion into GDP‐fucose. Fucose ( 1 ) was converted into ß‐ L ‐fucose‐1‐phosphate ( 2 ) with fucose kinase (EC 2.7.1.52) obtained from porcine submaxillary glands by consumption of ATP. Syntheses carried out with the enzymes enclosed in a dialysis bag gave 19% yield of ß‐ L ‐fucose‐1‐phosphate. Application of the enzymes in a batch procedure using an ultrafiltration cell gave 40% yield of the fucose‐1‐phosphate. The yield could be increased to 80% if the inhibitor ADP was removed by cofactor regeneration with phosphoenolpyruvate. ß‐ L ‐Fucose‐1‐phosphate was isolated as various salts and analyzed by NMR spectroscopy. In a second enzymatic reaction ß‐ L ‐fucose‐1‐phosphate was converted into GDP‐fucose ( 3 ) by the action of GDP‐fucose pyrophosphorylase (EC 2.7.7.30) obtained from porcine submaxillary glands. In a 50‐μmolar scale reaction, yields around 20% were obtained.