Download PDF
Synlett 1998; 1998(2): 201-205
DOI: 10.1055/s-1998-1599
letter
© 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.

Approaching the C33-C38 Fragments of Amphotericin B and Nystatin by a Retro-[1,4]-Brook Rearrangement and the Stereoselective Manipulation of the Resulting Allylsilane

Christoph Gibson* , Thomas Buck, Martina Walker, Reinhard Brückner
  • *Institut für Organische Chemie, Georg-August-Universität, Tammannstr. 2, D-37077 Göttingen, Germany; Fax +49-5 51-39 29 44; E-mail: rbrueck@gwdg.de
Further Information

Publication History

Publication Date:
31 December 2000 (online)

  PDF Download  Permissions and Reprints All articles of this category

Sulfide S-4 (98.6% ee) furnished allylsilane S,S-anti-2 through a potassium naphthalenide induced, highly stereoselective retro-Brook rearrangement. Treatment with diethylborane followed by NaOOH/H2O2 delivered alcohol 9 as a single diastereomer. Cylization (→ 10), oxidation (→ 16), and methylation gave ketone 17. Reduction of 17 with Et3SiH in CF3CO2H was accompanied by an unprecedented rearrangement of the neighboring oxasilolane ring to the C-silylated tetrahydropyran 20. It was oxidized to alcohol 21 which - if one inverted its OH group - would become a new C33-C38 building block for the polyol/polyene antibiotics amphotericin B and nystatin.

diastereoselectivity - alkylation - hydroboration - oxasilolane - Tamao oxidation

      >