Reactions of enantiopure cyclic diols with sulfuryl chloride

Derek R. Boyd, Narain D. Sharma, Magdalena Kaik, Peter B. A. McIntyre, John F. Malone, Paul J. Stevenson*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

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.



Original languageEnglish
Pages (from-to)2128-2136
Number of pages9
JournalOrganic and Biomolecular Chemistry
Volume12
Issue number13
DOIs
Publication statusPublished - 26 Feb 2014

Keywords

  • CHEMOENZYMATIC TOTAL-SYNTHESIS
  • ARENE OXIDATION-PRODUCT
  • OSELTAMIVIR PHOSPHATE TAMIFLU
  • EPOXIDE-OPENING REACTION
  • NUCLEOPHILIC-SUBSTITUTION
  • DOUBLE INVERSION
  • GAMMA,DELTA-EPOXY-ALPHA,BETA-UNSATURATED ESTERS
  • ASYMMETRIC DIHYDROXYLATION
  • MONOSUBSTITUTED BENZENES
  • (-)-SHIKIMIC ACID

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