title: Reactions of enantiopure cyclic diols with sulfuryl chloride.
abstract: Monocyclic allylic cis-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 trans-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 trans-azidohydrin without evidence of allylic rearrangement occurring. An enantiopure bicyclic cis-1,2-diol reacted with sulfuryl chloride to give, exclusively, a trans-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.
authors.affiliation: School of Chemistry and Chemical Engineering, Queens University, Belfast, N Ireland BT9 5AG, UK. p.stevenson@qub.ac.uk.
authors.forename: Derek R
authors.initials: DR
authors.lastname: Boyd
authors.forename: Narain D
authors.initials: ND
authors.lastname: Sharma
authors.forename: Magdalena
authors.initials: M
authors.lastname: Kaik
authors.forename: Peter B A
authors.initials: PB
authors.lastname: McIntyre
authors.forename: John F
authors.initials: JF
authors.lastname: Malone
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Stevenson
mesh_terms: D018360:Crystallography, X-Ray; D006018:Glycols / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D013441:Sulfinic Acids / Q000737:chemistry*; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D006018:Glycols; D013441:Sulfinic Acids; D013451:Sulfonic Acids