Concise chemoenzymatic synthesis of methyl d-2,3-dideoxyriboside

The synthesis of methyl α- and β-d-2,3-dideoxyriboside from a non-carbohydrate source is presented. The source of chirality is the microbial oxidation of halobenzenes to produce cyclohexadienediols, which are transformed into the final product in five steps with high chemical and enantiomeric purity.

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Methyl β-d-2,3-dideoxyribosideC6H12O3Ee = >99%[α]D23=-115 (c 0.1, CHCl3)Source of chirality: microbial oxidationAbsolute configuration: (1R,4S)

Methyl α-d-2,3-dideoxyribosideC6H12O3Ee = >99%[α]D23=+142 (c 0.2, CHCl3)Source of chirality: microbial oxidationAbsolute configuration: (1S,4S)

Methyl α-d-2,3-dideoxyglucofuranosideC7H14O4Ee = >99%[α]D23=+45 (c 0.8, CHCl3)Source of chirality: microbial oxidationAbsolute configuration: (1S,4S,5R)

Methyl β-d-2,3-dideoxyglucofuranosideC7H14O4Ee = >99%[α]D23=-37 (c 0.9, CHCl3)Source of chirality: Microbial oxidationAbsolute configuration: (1R,4S,R)

Methyl β-d-5,6-O-diacetyl-2,3-dideoxyglucofuranosideC11H18O6Ee = >99%[α]D23=-21 (c 0.9, CHCl3)Source of chirality: Microbial oxidationAbsolute configuration: (1R,4S,5R)

Methyl α-d-5,6-O-diacetyl-2,3-dideoxyglucofuranosideC11H18O6Ee = >99%[α]D23=+50 (c 0.9, CHCl3)Source of chirality: Microbial oxidationAbsolute configuration: (1S,4S,5R)