Ring-closing metathesis of α-ester-substituted enol ethers:: application to the shortest synthesis of KDO

Ring-closing metathesis reactions of alpha-ester-substituted enol ethers are described. In the case of unsubstituted terminal olefins, isomerization prior to cyclization was observed as an undesired side reaction, which could not be completely inhibited. Furthermore, this methodology was applied to a formal synthesis of KDO, which now represents the shortest synthetic pathway to KDO and its deoxy analogue. Interestingly, in this route olefin isomerization was not observed, presumably due to the increased steric environment of the double bond. Finally, an efficient two-step conversion to transform an alcohol into an alpha-alkoxy acrylate is also described. (C) 2003 Elsevier Ltd. All rights reserved.