The [3,3] rearrangement of 3-acetoxy-2-methyl-1-nonene (1b), derivatized as the trimethylsiloxyvinyl ether, proceeds in moderate yield (ca. 53%) but with very high stereoselectivity (>98%) to give the β,γ-unsaturated acid 2a. Rearrangement of the tert-butyldimethylsiloxyvinyl ether derivative proceeds in higher yield (80%), also with very high stereoselectivity. This rearrangement has been used in a stereoselective synthesis of a terpenoid diol (8) found in the phermonal secretion of the queen butterfly, in six steps from geraniol.
ASJC Scopus subject areas
- Organic Chemistry