A study on the dihydroxylation of a series of conformationally 'locked' cyclohexenols is reported. The orientation of the hydroxy group (i.e. equatorial or axial) is crucial in determining the degree of diastereoselectivity observed during oxidation. In some cases, the use of hydrogen-bonding enables the stereoselective synthesis of syn triols and tetraols. This effect has been utilised in the synthesis of conduritol D: X-ray crystal structure analysis provided a method of assigning the relative and absolute stereochemistry of an advanced synthetic intermediate.
