Ruthenium Catalysis in Biological Habitats

Abstract

Recent years have witnessed a considerable progress in research aimed at merging transition metal catalysis with chemical and cell biology. Therefore, a crescent number of metal-catalyzed transformations have been shown compatible with biological media and even with living settings. Of the different transition metals used to build these biocompatible catalysts, ruthenium has demonstrated to be particularly powerful, in part because the resulting complexes exhibit a very good balance between reactivity and biological stability. Indeed, ruthenium complexes have demonstrated utility to promote a great variety of reactions in biologically relevant contexts, from deprotection and redox processes to cycloadditions or photocatalytic transformations. Many of these reactions may enable the development of new type of biological tools and pharmacological strategies.

Cu-Catalyzed Azide–Alkyne–Thiol Reaction Forms Ubiquitous Background in Chemical Proteomic Studies

“…The latter option is similar to the previously described Ru-catalyzed cycloaddition. 37 However, under given conditions, weak or no labeling was observed for probes 1, 2, and 4. Taken together, the thiotriazole product forms under a wide variety of conditions, modifying the protein-free cysteines and proposing a mechanism (Figure S26) based on the experiments and literature.…”

“…To elucidate further the mechanism of the reaction, we have explored the possibility that either the triazole or the thioalkyne adduct is formed first and reacts subsequently with a thiol or azide in a Cu-catalyzed manner (Figure S25A,B). The latter option is similar to the previously described Ru-catalyzed cycloaddition . However, under given conditions, weak or no labeling was observed for probes 1 , 2, and 4 .…”

Ruthenium-catalyzed intermolecular alkene–alkyne couplings in biologically relevant media

“…Overall, the observed efficiencies compare favorably with other bioorthogonal reactions catalyzed by ruthenium complexes, such as the hydrosylilation of alkynes or alkene cross metatheses. 14 …”

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

“…[6] However, its improved catalytic performance vs. complex 1 in biological media has been a matter of debate. [20,26] Importantly, [CpRu IV (HQ)(η 3 -allyl)] + complexes have been reported to be cytotoxic in vivo. [17,18] In this study, we set out to investigate how the presence of GSH, O 2 , and the nature of the co-solvent affect the activity and the stability of [CpRu II (NMe 2 -QA)(solv)] 1, using the coumarin derivative 5 as substrate.…”