Nanostructured catalysts for organic transformations.

The development of green, sustainable and economical chemical processes is one of the major challenges in chemistry. Besides the traditional need for efficient and selective catalytic reactions that will transform raw materials into valuable chemicals, pharmaceuticals and fuels, green chemistry also strives for waste reduction, atomic efficiency and high rates of catalyst recovery. Nanostructured materials are attractive candidates as heterogeneous catalysts for various organic transformations, especially because they meet the goals of green chemistry. Researchers have made significant advances in the synthesis of well-defined nanostructured materials in recent years. Among these are novel approaches that have permitted the rational design and synthesis of highly active and selective nanostructured catalysts by controlling the structure and composition of the active nanoparticles (NPs) and by manipulating the interaction between the catalytically active NP species and their support. The ease of isolation and separation of the heterogeneous catalysts from the desired organic product and the recovery and reuse of these NPs further enhance their attractiveness as green and sustainable catalysts. This Account reviews recent advances in the use of nanostructured materials for catalytic organic transformations. We present a broad overview of nanostructured catalysts used in different types of organic transformations including chemoselective oxidations and reductions, asymmetric hydrogenations, coupling reactions, C-H activations, oxidative aminations, domino and tandem reactions, and more. We focus on recent research efforts towards the development of the following nanostructured materials: (i) nanostructured catalysts with controlled morphologies, (ii) magnetic nanocomposites, (iii) semiconductor-metal nanocomposites, and (iv) hybrid nanostructured catalysts. Selected examples showcase principles of nanoparticle design such as the enhancement of reactivity, selectivity and/or recyclability of the nanostructured catalysts via control of the structure, composition of the catalytically active NPs, and/or nature of the support. These principles will aid researchers in the rational design and engineering of new types of multifunctional nanocatalysts for the achievement of green and sustainable chemical processes. Although the past decade has brought many advances, there are still challenges in the area of nanocatalysis that need to be addressed. These include loss of catalytic activity during operation due to sintering, leaching of soluble species from the nanocatalysts under harsh reaction conditions, loss of control over well-defined morphologies during the scale-up synthesis of the nanocomposites, and limited examples of enantioselective nanocatalytic systems. The future of nanocatalyst research lies in the judicious design and development of nanocomposite catalysts that are stable and resistant to sintering and leaching, and yet are highly active and enantioselective for the desired catalytic organic transformations, even after multiple runs. The successful generation of such multifunctional nanocatalysts especially in tandem, domino, or cascade reactions would provide a powerful tool for the establishment of green and sustainable technologies.