Versatile diastereoselectivity in formal [3,3]-sigmatropic shifts of substituted 1-alkenyl-3-alkylidenecyclobutanols and their silyl ethers

A new method for the preparation of highly substituted cyclohexenones is reported. [2 + 2] Cycloaddition of 2-silyloxydienes with allenecarboxylate affords the 1-alkenyl-3-alkylidenecyclobutanol silyl ethers. Thermolysis of these compounds affords the methylene cyclohexenyl silyl ethers with excellent exo selectivity (>95:5) when monosubstituted alkenyl groups are used, while the use of disubstituted alkenyl groups gives generally low selectivity (∼2:1). However, rearrangement of the anion of the cyclobutanol (prepared by acidic hydrolysis of the TMS silyl ether) at low temperature gives the endo product with good to excellent diastereoselectivity (5-23:1). Two different mechanistic rationales are given for the two different processes: the first via a diradical and the second via a cleavage intramolecular Michael addition. Thus, the same starting material (e.g., 20) can be converted into either the exo or endo product, 22x or 22n, with good diastereocontrol by just changing the rearrangement conditions. Copyright © 2005 American Chemical Society.