title: Efficient chemoenzymatic synthesis of ADP-D-glycero-beta-D-manno-heptose and a mechanistic study of ADP-L-glycero-D-manno-heptose 6-epimerase.
abstract: [reaction: see text] A chemoenzymatic synthesis of ADP-D-glycero-beta-D-manno-heptose (ADP-D,D-Hep) is described in which D,D-Hep 7-phosphate is converted to ADP-D,D-Hep by two biosynthetic enzymes. This strategy allows access to the 6''-deuterated analogue, which upon incubation with the epimerase showed complete retention of the isotopic label at the 6''-position. This provides evidence for a direct oxidation mechanism in which the hydride initially transferred to the NADP+ cofactor is subsequently returned to the same carbon in a nonstereospecific manner.
authors.affiliation: Department of Chemistry, University of British Columbia, Vancouver, BC, Canada.
authors.forename: Jay A
authors.initials: JA
authors.lastname: Read
authors.forename: Raef A
authors.initials: RA
authors.lastname: Ahmed
authors.forename: Martin E
authors.initials: ME
authors.lastname: Tanner
mesh_terms: D000247:Adenosine Diphosphate Sugars / Q000138:chemical synthesis*; D002238:Carbohydrate Epimerases / Q000737:chemistry* / Q000378:metabolism*; D015394:Molecular Structure; D009249:NADP / Q000378:metabolism; D010084:Oxidation-Reduction; D010710:Phosphates / Q000378:metabolism; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000247:Adenosine Diphosphate Sugars; D010710:Phosphates; D009249:NADP; C031557:adenosine 5'-diphosphate-glycero-mannoheptose; C037213:ADP-L-glycero-D-mannoheptose-6-epimerase; D002238:Carbohydrate Epimerases