Download PDF
Synlett 1997; 1997(1): 11-21
DOI: 10.1055/s-1997-3729
account
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or commercialization outside the narrow limits set by copyright legislation, without the publisher's consent, is illegal and liable to criminal prosecution. This applies in particular to photostat reproduction, copying, cyclostyling, mimeographing or duplication of any kind, translating, preparation of microfilms, and electronic data processing and storage.

Lewis Acid Induced Rearrangement of 1-Hetero-2,3-Epoxides. Synthesis, Reactivity and Synthetic Applications of Homochiral Thiiranium and Aziridinium Ion Intermediates

Christopher M. Rayner*
  • *School of Chemistry, University of Leeds, Leeds LS2 9JT, U.K.; email: chrisr@chem.leeds.ac.uk
Further Information

Publication History

Publication Date:
22 March 2004 (online)

  PDF Download  Permissions and Reprints All articles of this category

2,3-Epoxy sulfides and 2,3-epoxy amines, prepared in an optically active form via the Sharpless asymmetric epoxidation, both undergo a Lewis acid induced rearrangement to give the corresponding thiiranium and aziridinium ions respectively. These reactive intermediates, generated in situ, react efficiently with a variety of nucleophiles such as silylated aromatic heterocycles, amides, and amines, including amino acid derivatives. Imines can be used as synthetic equivalents of primary amine nucleophiles, which effectively allows selective monoalkylation with a reactive thiiranium ion intermediate. Applications of this new methodology, and mechanistic studies are also discussed.

epoxy alcohol - thiiranium ion - aziridinium ion - β-hydroxy sulfide - β-amino alcohol - amino acid - bestatin