Construction of Fused Medium-Ring Carbocycles by Catalytic Generation and Rearrangement of Oxonium Ylides

✍ Scribed by J. Stephen Clark; Steven B. Walls; Claire Wilson; Stephen P. East; Martin J. Drysdale

• Book ID: 102175822
• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 125 KB
• Volume: 2006
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/ejoc.200500830

✦ Synopsis

Abstract

Fused carbocyclic systems containing seven‐ and eight‐membered rings can be constructed from allylic ethers in a stereoselective manner by tandem carbenoid generation, ylide formation and [2,3] rearrangement. Exceptionally high yields are obtained in cases where the substrate possesses favourable relative stereochemistry. The dienes resulting from [2,3] rearrangement of gem‐divinyl ylides undergo Diels–Alder cycloaddition with reactive dienophiles at room temperature. Ylide formation, rearrangement and cycloaddition can be performed in a one‐pot process to generate complex tetracyclic systems in a highly stereoselective manner. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)