1,5-Anhydro-D-fructose; a versatile chiral building block: biochemistry and chemistry.
There is a steadily increasing need to expand sustainable resources, and carbohydrates are anticipated to play an important role in this respect, both for bulk and fine chemical preparation. The enzyme alpha-(1-->4)-glucan lyase degrades starch to 1,5-anhydro-D-fructose. This compound, which has three different functional properties, a prochiral center together with a permanent pyran ring, renders it a potential chiral building block for the synthesis of valuable and potentially biologically active compounds. 1,5-Anhydro-D-fructose is found in natural materials as a degradation product of alpha-(1-->4)-glucans. The occurrence of lyases and the metabolism of 1,5-anhydro-D-fructose are reviewed in the biological part of this article. In the chemical part, the elucidated structure of 1,5-anhydro-D-fructose will be presented together with simple stereoselective conversions into hydroxy/amino 1,5-anhydro hexitols and a nojirimycin analogue. Synthesis of 6-O-acylated derivatives of 1,5-anhydro-D-fructose substituted with long fatty acid residues is carried out using commercially available enzymes. Those reactions lead to compounds with potential emulsifying properties. The use of protected derivatives of 1,5-anhydro-D-fructose for the synthesis of natural products is likewise reviewed. The potential utilization of this chemical building block is far from being exhausted. Since 1,5-anhydro-D-fructose now is accessible in larger amounts through a simple-enzyme catalyzed degradation of starch by alpha-(1-->4)-glucan lyase, the application of 1,5-anhydro-D-fructose may be considered a valuable contribution to the utilization of carbohydrates as the most abundant resource of sustainable raw materials.
Andersen
Søren M
SM
Department of Chemistry, Technical University of Denmark, Building 201, DK-2800 Kgs., Lyngby, Denmark.
Lundt
Inge
I
Marcussen
Jan
J
Yu
Shukun
S
D000818:Animals; D002240:Carbohydrate Sequence; D005632:Fructose / Q000031:analogs & derivatives* / Q000096:biosynthesis / Q000737:chemistry* / Q000378:metabolism* / Q000633:toxicity; D006801:Humans; D006863:Hydrogen-Ion Concentration; D008190:Lyases / Q000378:metabolism; D008969:Molecular Sequence Data; D010084:Oxidation-Reduction; D013213:Starch / Q000096:biosynthesis / Q000378:metabolism
D005632:Fructose; C048927:1,5-anhydrofructose; D013213:Starch; D008190:Lyases