Cationic cyclization of keto-epoxides mediated by zirconium(IV) tetrachloride: diastereoselective synthesis of cis-decalinols

Abstract

10-Methyl- cis-9-decalinols are important motifs in several natural products and key intermediates in total synthesis. Herein, we wish to describe a highly chemo- and diastereoselective cyclization of keto-epoxides leading to 10-methyl- cis-9-decalinols. This method based on the use of zirconium(IV) tetrachloride permits the access to a wide variety of cis-decalinols in good to excellent yields. The cationic cyclization could also be performed with chiral keto-epoxide with complete control of the diastereoselectivity affording cis-bicyclic tertiary alcohol with good enantiomeric excess. The chemo- and the diastereoselectivity are assumed to result from the ability of Zr(IV) to generate highly stable bidentic complexes with α-hydroxy-ketone intermediates.