Reactions of enantiopure cyclic diols with sulfuryl chloride

<p>Monocyclic allylic <em>cis</em>-1,2-diols reacted with sulfuryl chloride at 0 °C in a regio- and stereo-selective manner to give 2-chloro-1-sulfochloridates, which were hydrolysed to yield the corresponding <em>trans</em>-1,2-chlorohydrins. At −78 °C, with very slow addition of sulfuryl chloride, cyclic sulfates were formed in good yields, proved to be very reactive with nucleophiles and rapidly decomposed on attempted storage. Reaction of a cyclic sulfate with sodium azide yielded a <em>trans</em>-azidohydrin without evidence of allylic rearrangement occurring. An enantiopure bicyclic <em>cis</em>-1,2-diol reacted with sulfuryl chloride to give, exclusively, a <em>trans</em>-1,2-dichloride enantiomer with retention of configuration at the benzylic centre and inversion at the non-benzylic centre; a mechanism is presented to rationalise the observation.</p><p><br/><br/></p>