On possible redirection of the course of anionic oxy-cope rearrangements

✍ Scribed by Leo A. Paquette; Donald T. DeRussy; Robin D. Rogers

• Publisher: Elsevier Science
• Year: 1988
• Tongue: French
• Weight: 921 KB
• Volume: 44
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)85945-7

✦ Synopsis

The p,r-unsaturated ketonea bicyclo[2.2.l]hspt-2-en-7-one (10) and 7,7-dimethoxybicyclo[2.2.l]hept-2-en-S-one (15) have been condensed with lmetalated trans-l-•ethoxybutadienea (7a or 7b) and 2-isopropenylcyclopentenea (8b or 8~). Oxyanion formation within the resulting alcohols is followed by skeletal rearrangement at room temperature. Careful product analysis has revealed the [3,3) sigmatropic reaction manifold to be folloved almost exclusively, Only in the case of 13 is a modest amount (48) of formal antarafacialretention [1,3] sigmatropic bridgehead carbon migration in evidence. Consequently, the structural features inherent to these alcohols are not conducive to redirecting electronic reorganization to an alternative isomerizatlon process.