Stereoselective Construction of cis-26-Disubstituted Tetrahydropyrans via the Reductive Etherification of δ-Trialkylsilyloxy Substituted Ketones: Total Synthesis of (—)-Centrolobine

摘要

The stereoselective intramolecular reductive etherification of δ-trialkylsilyloxy substituted ketones with catalytic bismuth tribromide and triethylsilane provides a convenient method for the construction of cis-2,6-disubstituted tetrahydropyrans. This method was highlighted in the key step of an expeditious total synthesis of the antibiotic, (—)-centrolobine.