radical oxidative cyclization of spiroacetals to bis-spiroacetals an overview自由基氧化环合spiroacetals bis-spiroacetals概述.pdfVIP

Molecules 2004, 9, 394-404 molecules ISSN 1420-3049 Radical Oxidative Cyclization of Spiroacetals to Bis-spiroacetals: An Overview Margaret A. Brimble* Department of Chemistry, University of Auckland, 23 Symonds St., Auckland, New Zealand. Tel. (+64) 9-3737599 ext 88259, Fax (+64) 9-3737422. * Author to whom correspondence should be addressed; e-mail m.brimble@auckland.ac.nz Received: 18 December 2003 / Accepted: 3 January 2004 / Published: 31 May 2004 Abstract: The use of iodobenzene diacetate and iodine under photolytic conditions provides and efficient method for the oxidative cyclization of spiroacetals bearing an hydroxyalkyl side chain to bis-spiroacetals. An overview is provided of the use of this reaction for the synthesis of several bis-spiroacetal containing natural products such as the polyether antibiotics salinomycin and CP44,161 and the shellfish toxins, the spirolides. Keywords: Spiroacetals, bis-spiroacetals, oxidative radical cyclization Introduction Tricyclic bis-spiroacetal ring systems are present as sub-units in a diverse range of natural products and have attracted attention from synthetic chemists due to their stereochemical complexity and variety in their biological activity. Several reviews on the chemistry of more common bicyclic spiroacetals have been published [1] and reviews on the chemistry of bis-spiroacetals have also been forthcoming [2]. Many of the synthetic methods adopted for the construction of spiroacetals rely on the control of stereochemistry at the anomeric