The Two Janus Faces of CpRu‐Based Deallylation Catalysts and Their Application for in Cellulo Prodrug Uncaging

Abstract

In the past 18 years, metal‐catalyzed deallylation has proven a useful tool for studying biological processes in cellulo and in the early development of innovative therapeutic catalytic strategies. This reaction is catalyzed by Ru‐piano stool complexes and has been reported to be compatible with air, water, and thiol‐containing compounds such as glutathione. However, little is known about the true influence of biological components on the outcome of this reaction. The results presented herein reveal that the co‐solvent used in the reaction affects the complex’s stability and activity in air, while the presence of glutathione contributes to minimizing the formation of N‐allylated by‐products. In addition, we studied the effect of air on the Ru‐catalyzed deallylation. Importantly, we found that, in the presence of air, the complex is deactivated and oxidizes glutathione into its disulfide.