External link: https://pubs.rsc.org/en/content/articlelanding/2023/CB/D3CB00053B

Abstract: The ability to perform 'new-to-nature' chemical reactions within living cells and organisms is transforming the way in which scientists interrogate and/or manipulate biological processes. In recent years, the toolbox of bioorthogonal and cell-compatible reactions has been enriched with the incorporation of transition metal-mediated processes. Whereas the efficiency of these reactions is still low, the breadth and generality of organometallic catalysis promises to significantly impact the field of bioorthogonal chemistry. Particularly attractive is the possibility of using organometallic catalysis for performing bond-forming, synthetically relevant reactions, as this could allow assembly of biorelevant products at specific biological sites.

External link: https://www.sciencedirect.com/science/article/pii/S2589597423000916

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.

External link: https://onlinelibrary.wiley.com/doi/abs/10.1002/hlca.202300001

Abstract: Iridium-catalyzed borylations of aromatic C–H bonds are highly attractive transformations owing to the diversification possibilities offered by the resulting boronates. These transformations are best carried out using bidentate bipyridine or phenanthroline ligands, and tend to be governed by steric factors, therefore resulting in the competitive functionalization of meta and/or para positions. We have now discovered that a subtle change in the bipyridine ligand, namely, the introduction of a CF3 substituent at position 5, enables a complete alteration of regioselectivity in the borylation of aromatic amides, providing for the synthesis of a wide variety of ortho-borylated derivatives. Importantly, thorough computational studies suggest that the exquisite regio- and chemoselectivity stems from unusual outer-sphere interactions between the amide group of the substrate and the CF3–substituted aryl ring of the bipyridine ligand.

External link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202214510