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Synlett 1998; 1998(2): 201-205
DOI: 10.1055/s-1998-1599
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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
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Publikationsdatum:
31. Dezember 2000 (online)

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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