Stereoselective Synthesis of 1,n‐Dicarbonyl Compounds Through Palladium‐Catalyzed Ring Opening/Isomerization of Densely Substituted Cyclopropanols

Abstract

We report a highly diastereoselective protocol for the synthesis of 1,4‐ and 1,5‐dicarbonyl compounds from densely substituted cyclopropanols. The methodology involves a palladium‐catalyzed ring opening reaction followed by a “metal‐walk” and oxidation of a remote hydroxyl group. The methodology represents a new application of cyclopropanols as initiation sites for chain walking remote functionalization. Importantly, this approach provides a straightforward access to highly valuable succinaldehyde derivatives bearing vicinal quaternary and tertiary stereocenters as single diastereomers.