recent synthetic approaches toward non-anomeric spiroketals in natural products最近的合成方法对non-anomeric spiroketals自然产品.pdfVIP

Molecules 2008, 13, 2570-2600; DOI: 10.3390/molecule OPEN ACCESS molecules ISSN 1420-3049 /molecules Review Recent Synthetic Approaches Toward Non-anomeric Spiroketals in Natural Products Sylvain Favre, Pierre Vogel and Sandrine Gerber-Lemaire* Laboratory of Glycochemistry and Asymmetric Synthesis, Ecole Polytechnique Fédérale de Lausanne, Batochime, CH-1015 Lausanne, Switzerland * Author to whom correspondence should be addressed; E-mail: Sandrine.Gerber@epfl.ch. Received: 18 July 2008; in revised form: 29 September 2008 / Accepted: 15 October 2008 / Published: 17 October 2008 Abstract: Many natural products of biological interest contain [6,5]- and [6,6]-spiroketal moieties that can adopt various configurations, benefiting or not from anomeric conformation stabilizing effects. The spiroketal fragments are often important for the biological activity of the compounds containing them. Most stable spiroketal stereoisomers, including those benefiting from conformational anomeric effects (gauche conformers can be more stable than anti conformers because of a contra-steric stabilizing effect), are obtained easily under acidic conditions that permit acetal heterolysis (formation of tertiary oxycarbenium ion intermediates). The synthesis of less stable stereoisomers requires stereoselective acetal forming reactions that do not permit their equilibration with their most stable stereoisomers or, in