Triisobutylaluminium (TIBAL) Promoted Rearrangement of C-glycosides 英文参考文献.docVIP

Molecules 2005, 10, 843-858 molecules ISSN 1420-3049 Triisobutylaluminium (TIBAL) Promoted Rearrangement of C-glycosides Matthieu Sollogoub* and Pierre Sina? Ecole Normale Supérieure, Département de Chimie, UMR 8642 : CNRS-ENS-UPMC Paris 6, 24 rue Lhomond, 75231 Paris Cedex 05, France; http://www.chimie.ens.fr/UMR8642/Glycoscience/index.html * Author to whom correspondence may be addressed; e-mails: Matthieu.Sollogoub@ens.fr Received: 8 October 2004; in revised form: 4 November 2004 / Accepted: 10 November 2004 Published: 31 August 2005 Abstract: Triisobutylaluminium-promoted rearrangement of unsaturated glycosides containing electron-donating aglycons, such as C-aryl glycosides, provides direct access to highly functionalised cyclohexane derivatives. Keywords: Carbohydrates, C-glycosides, carbocycles, rearrangements Introduction The conversion of carbohydrates into carbocycles provides a powerful method for the preparation of highly functionalised enantiomerically pure carbocycles. The pyranose-cyclohexane conversion has received particular attention due to the myriad of bioactive substances such as aminocyclitols, inositols and carbasugars, which are attainable. Among those a more complex one has attracted particular attention: pancratistatine [1-3] (Figure 1). It is a polyfunctionalised cyclohexane directly connected to an aromatic ring. The classical Ferrier-II reaction [2] involving Hg(II) catalysed rearrangement of readily available hex-5-enopyranosides into cyclohexanones has, thus far, been the most widely exploited. In 1997 we reported that the same starting material used for the Ferrier-II reaction, carbohydrate based vinyl acetals (hex-5-enopyranosides) such as 1, undergo smooth reductive rearrangement with triisobutylaluminium (TIBAL) to afford highly functionalized cyclohexanes such as 2 (Scheme 1) [3].  Molecules 2005, 10 844 Figure 1 HO HO OH OH O O NH O OH (+)-pancratistatine In sharp c