Studies on the biosynthesis of the alpha-glucosidase inhibitor acarbose: valienamine, a m-C7N unit not derived from the shikimate pathway.
Feeding experiments with Actinoplanes sp. SN223/29 showed that 3-amino-5-hydroxy-[7-13C]benzoic acid is not incorporated into acarbose (I). The valienamine moiety of I is thus not derived in the same way, from the shikimate pathway, as the m-C7N units in the ansamycin, mitomycin and ansamitocin antibiotics. Feeding experiments with [U-13C3]-glycerol followed by analysis of I by multiple quantum NMR spectroscopy support this conclusion and point to formation of the valienamine moiety by cyclization of a heptulose phosphate which arises from a triose phosphate via successive transfer of two 2-carbon fragments by transketolase, as proposed by Pape and co-workers.
Degwert
U
U
van Hülst
R
R
Pape
H
H
Herrold
R E
RE
Beale
J M
JM
Keller
P J
PJ
Lee
J P
JP
Floss
H G
HG
D020909:Acarbose; D000192:Actinomycetales / Q000378:metabolism; D055598:Chemical Phenomena; D002621:Chemistry; D053138:Cyclohexenes; D005990:Glycerol / Q000378:metabolism; D065089:Glycoside Hydrolase Inhibitors; D006595:Hexosamines / Q000096:biosynthesis*; D009682:Magnetic Resonance Spectroscopy; D012765:Shikimic Acid / Q000378:metabolism*; D014312:Trisaccharides / Q000096:biosynthesis*
D053138:Cyclohexenes; D065089:Glycoside Hydrolase Inhibitors; D006595:Hexosamines; D014312:Trisaccharides; D012765:Shikimic Acid; C030791:valienamine; D005990:Glycerol; D020909:Acarbose