Concise asymmetric syntheses of the (+)-2-C-methyltetritol isomers

Two brief and facile syntheses of the title compounds have been developed using the diastereocontrolled addition of organometallics to a (R)-cyclohexylideneglyceraldehyde-derived ketone as the key steps. The addition of vinylmagnesium bromide to the ketone gave a 1:1 diastereomeric mixture of separable tertiary alcohols, which were converted to the target erythri- and threitols. On the other hand, the reaction of a dithianyl anion with the ketone gave only the single stereoisomer of a tertiary alcohol, which was converted to erythritol.

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(3R)-3,4-Cyclohexanedioxybutan-2-oneC10H16O3C10H16O3[α]D22=+32.0 (c 1.62, CHCl3)Source of chraility: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (3R)

(3R,4R)-4,5-Cyclohexanedioxy-3-methylpent-1-en-3-olC12H20O3C12H20O3[α]D22=+11.3 (c 1.12, CHCl3)Source of chraility: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (3R,4R)

(3S,4R)-4,5-Cyclohexanedioxy-3-methylpent-1-en-3-olC12H20O3C12H20O3[α]D22=+20.6 (c 1.04, CHCl3)Source of chraility: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (3S,4R)

(2S,3R)-3,4-Cyclohexanedioxy-2-methyl-2-hydroxybutanalC11H18O4C11H18O4[α]D22=+16.05 (c 1.52, CHCl3)Source of chraility: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (2S,3R)

(2R,3R)-3,4-Cyclohexanedioxy-2-hydroxy-2-methylbutanalC11H18O4C11H18O4[α]D22=+18.1 (c 1.14, CHCl3)Source of chirality: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (2R,3R)

(2R,3R)-3,4- Cyclohexanedioxy-2-methylbutane-1,2-diolC11H20O4C11H20O4[α]D22=+11.6 (c 1.02, CHCl3)Source of chirality: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (2R,3R)

(2S,3R)-3,4-Cyclohexanedioxy-2-methylbutane-1,2-diolC11H20O4C11H20O4[α]D22=+12.8 (c 1.72, CHCl3)Source of chirality: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (2S,3R)

(2R,3R)-2-Methylbutane-1,2,3,4-tetrolC5H12O4C5H12O4[α]D22=+11.2 (c 1.41, MeOH)Source of chirality: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (2R,3R)

(2S,3R)-2-Methylbutane-1,2,3,4-tetrolC11H20O4C11H20O4[α]D22=+15.0 (c 1.44, MeOH)Source of chirality: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (2S,3R)

(2S,3R)-3,4-Cyclohexanedioxy-2-methyl-2-(1′,3′-propanediyldithio)butan-2-olC14H24O3S2C14H24O3S2[α]D22=+12.45 (c 2.86, CHCl3)Source of chirality: (R)-cyclohexylideneglyceraldehydeAbsolute configuration: (2S,3R)