Synthesis and Reactivity of Enantiomerically Enriched Thiiranium Ions

Enantiomerically enriched thiiranium ion 5 has been prepared by silver‐assisted ionization of chloro sulfide 4 at −20 °C. This thiiranium ion is configurationally stable in solution up to room temperature as demonstrated by the stereospecific capture of the ion by various oxygen‐ and nitrogen‐based...

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Bibliographic Details
Published in:Chemistry : a European journal 2009-11, Vol.15 (43), p.11737-11745
Main Authors: Denmark, Scott E., Vogler, Thomas
Format: Article
Language:English
Subjects:
episulfonium ions
Lewis bases
nucleophiles
stereoselectivity
sulfur
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Summary:Enantiomerically enriched thiiranium ion 5 has been prepared by silver‐assisted ionization of chloro sulfide 4 at −20 °C. This thiiranium ion is configurationally stable in solution up to room temperature as demonstrated by the stereospecific capture of the ion by various oxygen‐ and nitrogen‐based nucleophiles. Both isolated olefins and weak Lewis bases can promote the racemization of 5 but these processes can also be suppressed at low temperature. Capture of 5 by methanol is faster than the racemization processes. Enantiomerically enriched thiiranium ions have been prepared by silver‐assisted ionization of chlorosulfide at −20 °C. The absolute configurational stability of the ions has been investigated in detail and these chiral, nonracemic thiiranium ions are found to be configurationally stable. The stereospecific trapping is also investigated (see scheme).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.200901377