Regioselective Base-induced Ethereal Bridge Openings of 7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic Derivatives; Synthesis of Squalestatin Core Analogues

Nathalie Jotterand; Pierre Vogel

doi:10.1055/s-1999-2965

Synlett 1999; 1999(12): 1883-1886
DOI: 10.1055/s-1999-2965

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.

Regioselective Base-induced Ethereal Bridge Openings of 7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic Derivatives; Synthesis of Squalestatin Core Analogues

Nathalie Jotterand^* , Pierre Vogel

^*Section de Chimie de l'Université, BCH, CH-1015 Lausanne-Dorigny, Switzerland; Fax + 412 16 92 39 75; E-mail: pierre.vogel@ico.unil.ch

Abstract

PDF Download All articles of this category

The Diels-Alder adduct of furfuryl alcohol and maleic anhydride was converted into dimethyl 5-exo,6-exo-dihydroxy-1-{[tris(isopropyl)silyloxy]methyl}-7-oxabicyclo[2.2.1]heptane-2-exo,3-exo-dicarboxylate (12). Regioselective monosilylation of diol 12 gave the 5-O-(tert-butyl)dimethylsilyl ether 18. Under basic conditions the 7-oxanorbornane system of 18 was isomerized selectively into a 4,5,6-trihydroxy-6-(hydroxymethyl)cyclohex-2-ene-1,2-dicarboxylic derivative that was converted into a doubly-branched hepturonic acid derivative (24), potential precursor for the preparation of squalestatin core analogues.

dioxoheptanoic acid - hepturonic acid - ketoester selective reduction - 7-oxabicyclo[2.2.1]heptane - oxepane - ozonolysis

PDF (97 kb)