Synthesis of a cis-5-cyclodecenone and cis fused hydronaphthalenols through control of the stereochemistry of the oxy-Cope rearrangement with the tri-n-propylsilyl substituent

✍ Scribed by Yongliang Chu; David Colclough; David Hotchkin; Myla Tuazon; James B. White

• Publisher: Elsevier Science
• Year: 1997
• Tongue: French
• Weight: 716 KB
• Volume: 53
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(97)00952-6

✦ Synopsis

In the course of preparing a trimethylsilyl substituted 5-cyclodocenone through anionic oxy-Cope reanangement of a trans-l,2-divinylcyclohexanol, it was discovered that the silyl substituent in the divinylcyelohexan01 is positioned so that it destabilizes [3,3]-sigmatropic reaffang~ent through the normally observed cha£r-like transition state. In the case of the ~n-propylsilyl derivative, oxy-Cop¢ rearrangement was observed to take place exclusively through the boat.like transition state to give (Ep5-(tri-n-propylsilyl)-5-cyclodecenone with the cis double bond with resp~ to the ring. Acid-induced Wansannular cycfizafion of the E isomer led to 1,6-cycfization and generation of the cis-fused hydronaphthalvnol.