Organometallic catalysis in biological media and living settings

Abstract

Organometallic catalysis has allowed the development of an impressive number of chemical transforma-28 tions that could not be achieved using classical methodologies. Most of these reactions have been accom-29 plished in organic solvents, and in many cases in the absence of water, and under air-free conditions. The 30 increasing pressure to develop more sustainable transformations has stimulated the discovery of metal-31 catalyzed reactions that can take place in water. A particularly attractive extension of this chemistry con-32 sists of the use of biological relevant aqueous solvents, as this might set the basis to translate catalytic 33 metal complexes to biological settings. While this research field is in its infancy, along the last ten years 34 there have been an increasing number of reports demonstrating the viability of achieving metal-35 promoted transformations in biologically relevant contexts. In this review, that does not intend to be 36 comprehensive, we summarize the most significant advances in the area, and highlight some of the more 37 important difficulties that must be faced when trying to design biocompatible organometallic catalysts, 38 such us stability, cell uptake, bioorthogonality and toxicity. We will manly focus on transition metal sys-39 tems which have been showed to keep their activity in complex aqueous buffers and inside living cells. 40

Catalysis Concepts in Medicinal Inorganic Chemistry

“…These processes, to date mostlyc leavage or cross-coupling reactions, use abiotic substratesa nd metal-based catalysts and can occur with remarkable efficiency and bioorthogonal selectivity. [5,6,10] Catalysts are administered at low concentrations, thus moderating metal toxicityconcerns.…”

“…An umber of recent review articles revise the achievements of catalytic metallodrugs and metal-based bioorthogonal catalysis. [1,[5][6][7][8][9][10][11] In this Concept article, we insteada im at picking out key examples and concepts that have laid the foundations for the use of catalysis in medicinal inorganic chemistrya nd relate them to recent discoveries obtained in our laboratory.T ot his end, we put our focuso nh ow innovative catalystd esign hypotheses have openedt on ew chemistries for application in therapy.…”

Reaction‐based AIE‐active Fluorescent Probes for Selective Detection and Imaging

“…Metal‐induced self‐assembling processes, such as metal complexion,, metallogelation,, and so on, can be considered as a special kind of metal‐mediated reactions. Recently, De Cola and Biedermann et al .…”

Visible Light Photoredox Catalysis Using Ruthenium Complexes in Chemical Biology

“…While transition metals are often associated with the well-known toxicity of anticancer drugs such as cis-platins, an umber of publications have demonstrated that there is an interesting windowo fo pportunity. [5][6][7] While the term bioorthogonal chemistry was initially coined for ligationr eactions, bond cleavage reactions are also of interesti nc hemicalb iology to uncage substrates, inhibitors or af unctionalg roup of interest. [8] Light is an attractive external stimulant to trigger such cleavagee vents since it can be controlled both in time andspace.Not surprisingly,photolabile groups to unmaskt he functiono famolecule with spatiotemporal control have been extensively used in chemical biology.…”