Silica‐Bound Homogenous Catalysts as Recoverable and Reusable Catalysts in Organic Synthesis

Very frequently the most costly components in a chemical reaction are not the starting materials or the reaction products, but the catalyst. In addition to the advantages from the economic point of view, recovery and reuse of the catalyst is equally important in order to avoid wastes, so improving the greenness of the process. There is a current tendency to transform homogeneous into heterogeneous catalysis, that will even be accelerated in the near future. Starting from a successful homogeneous catalyst, one general methodology allowing its recovery and reuse is to immobilize a suitable derivative of the active catalyst on an insoluble solid support. When the catalyst does not deactivate and is sufficiently stable under the reaction conditions, the ultimate immobilization methodology is to attach covalently the catalytically active species to the support. In this contribution, after introducing some general principles describing the fundamentals of the covalent anchoring, the emphasis is placed more on giving an overview of the most important types of covalently anchored catalysts, including Brönsted and Lewis acids, covalently anchored bases and hydrogenation complexes. Hot topics such as silica‐bound organocatalysts and the application of periodic mesoporous organosilicas as heterogeneous catalysts is also covered.