Late-Stage Molecular Editing Enabled by Ketone Chain-Walking Isomerization

[Image: see text] Herein, a method for the isomerization of ketones in a manner akin to the chain-walking reaction of alkenes is described. Widely available and inexpensive pyrrolidine and elemental sulfur are deployed as catalysts to achieve this reversible transformation. Key to the utility of this approach was the elucidation of a stereochemical model to determine the thermodynamically favored product of the reaction and the kinetic selectivity observed. With the distinct selectivity profile of our ketone chain-walking process, the isomerization of various steroids was demonstrated to rapidly access novel steroids with “unnatural” oxidation patterns.