Narrow Results

The catalytic functionalization of C–H, C–OH and C–C bonds belongs to the most important processes in nature and the industry. In nature, this process occurs via involvement of enzymes, effectively and selectively, usually with very high turnover numbers. The pivotal role in enzymatic activity is played by the metal center cofactors, which involve several bioavailable transition metals, such as, iron, copper, manganese and zinc. In the industry, bond functionalization requires the presence of metal catalysts; therefore, a bio-inspired design of metal catalysts is a challenging approach. The recent advances in the catalysis of industrially important reactions, namely the oxidation and hydrocarboxylation of alkanes, the oxidation of alcohols and C–C coupling are reported. Convenient, environmentally friendly methods are presented, and the role and efficacy of the various transition-metal (iron, copper, zinc, manganese, nickel, vanadium, palladium and cobalt) catalysts are explored.

The potential applications for heterogeneous catalysts (supported metallic complexes, metal–organic frameworks (MOFs) or polynuclear complexes) in C–H and C–OH activation are tantalizing. In response to the opportunity, novel strategies have been recently developed, which present a critical step toward harnessing the experimental factors, such as yield and selectivity, by enabling new techniques and hence real-world applications. This chapter provides an up-to-date survey (from the past five years) of the most promising novel routes by summarizing the progress made in the use of unconventional activation methods for performing oxidation reactions, highlighting the synergy of these technologies with heterogeneous catalysis. Focus is centered on both usual catalysts activation methods and less usual ones, such as ultrasounds, microwaves, grinding (mechanochemistry), as well as their combined use.