Processing of cyclopropylarenes by toluene dioxygenase: isolation and absolute configuration of metabolites

Several arenes possessing a cyclopropyl substituent were subjected to enzymatic oxidation with toluene dioxygenase. The absolute configuration of metabolites was established by chemical means.

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(1S,2R)-3-(1-Methyl-cyclopropyl)-cyclohexa-3,5-diene-1,2-diolC10H14O2Ee >95%[α]D26=+65 (c 1.0, MeOH)Source of chirality: enzymatic oxidationAbsolute configuration: (1S,2R)

(1R,2R)-3-Bromo-6-cyclopropyl-cyclohexa-3,5-diene-1,2-diolC9H11BrO2Ee = 27%[α]D24=-17.5 (c 0.65, CHCl3)Source of chirality: enzymatic oxidationAbsolute configuration: (1R,2R)

(3aR,7aS)-2,2-Dimethyl-4-propenyl-3a,4,5,7a-tetrahydro-benzo[1,3]dioxoleC12H18O2Ee >95%[α]D24=+68.1 (c 0.72, CHCl3)Source of chirality: enzymatic oxidationAbsolute configuration: (3R,7S)

(1S,2R)-3-Propenyl-cyclohex-3-ene-1,2-diolC9H14O2Ee >95%[α]D24=-133 (c 0.51, CHCl3)Source of chirality: enzymatic oxidationAbsolute configuration: (1S,2R)