2013 August 14; 113(8): 6234–6458 | Scott E. Allen, Ryan R. Walvoord, Rosaura Padilla-Salinas, and Marisa C. Kozlowski
The chemistry of copper is highly versatile due to its ability to access various oxidation states, allowing it to participate in both radical and two-electron bond-forming pathways. Oxygen, as an atom-economical and environmentally benign oxidant, is widely used in copper-catalyzed reactions. However, the high activation energies of oxygen reactions require catalysts, and the flammability of oxygen in batch reactors limits its use. Alternative approaches, such as using carbon dioxide or water, have been developed to mitigate these issues. Enzymatic systems and biomimetic systems have inspired the development of small molecule catalysts that can mimic the redox chemistry of enzymes. The study of copper-catalyzed oxidation chemistry using molecular oxygen has seen significant growth, with a focus on the oxidation of hydrocarbons, including benzyl, alkyl, alkenyl, alkynyl, and aryl groups. Key challenges include controlling the degree of oxygenation, achieving high selectivity, and developing more efficient catalysts. Recent advancements include the use of directed groups and the development of biomimetic systems, but significant progress is still needed to achieve broader applicability and industrial-scale use.The chemistry of copper is highly versatile due to its ability to access various oxidation states, allowing it to participate in both radical and two-electron bond-forming pathways. Oxygen, as an atom-economical and environmentally benign oxidant, is widely used in copper-catalyzed reactions. However, the high activation energies of oxygen reactions require catalysts, and the flammability of oxygen in batch reactors limits its use. Alternative approaches, such as using carbon dioxide or water, have been developed to mitigate these issues. Enzymatic systems and biomimetic systems have inspired the development of small molecule catalysts that can mimic the redox chemistry of enzymes. The study of copper-catalyzed oxidation chemistry using molecular oxygen has seen significant growth, with a focus on the oxidation of hydrocarbons, including benzyl, alkyl, alkenyl, alkynyl, and aryl groups. Key challenges include controlling the degree of oxygenation, achieving high selectivity, and developing more efficient catalysts. Recent advancements include the use of directed groups and the development of biomimetic systems, but significant progress is still needed to achieve broader applicability and industrial-scale use.