The selective oxidation of C-H bonds in (hetero)aromatics provides an efficient access to functionalized aromatic molecules of industrial interest. Aerobic oxygen is an ideal terminal oxidants for this transformation because it is readily available and often produces water as the sole byproduct. Homogeneous palladium catalysts are eminently compatible with aerobic turnovers and have seen success in numerous aerobic oxidation processes (e. g., alkene oxidation, alcohol oxidation). In contrast, palladium-catalyzed aerobic oxidative C-H functionalization has been rather underdeveloped. Challenges include slow catalytic turnover, catalyst decomposition and lack of selectivity control (e.g., site selectivity, homo- vs. cross-coupling selectivity). This thesis presents three research projects with different approaches to tackle the unsolved problems in the reaction class of palladium-catalyzed aerobic C-H oxidation of (hetero)aromatics. The reaction mechanism of C-H/C-H coupling of [o]-xylene was characterized, which disclosed a novel, bimetallic pathway. Built on this work, the effect of copper cocatalyst in this reaction was investigated, which revealed a non-traditional role of copper salt in oxidative palladium catalysis and led to the discovery of an improved catalyst system. Last, a synthetic methodology for aerobic indole C-H arylation with ligand-controlled site selectivity was developed, which provided efficient access to pharmaceutically-relevant aryl indoles and led to preliminary mechanistic insights into regiocontrol.

Oxidation reactions are an important chemical transformation in both academia and industry. Among the major advances in the field has been the development of catalytic processes, which are not only selective and efficient, but also allow the replacement of common stoichiometric oxidants with molecular oxygen, ideally from air at atmospheric pressure. This results in processes with higher atom efficiency, where water is the only side product in line with the principles of green chemistry. Focusing on the use of molecular oxygen as the terminal oxidant, this book covers recent advances in both heterogeneous and homogeneous systems, with and without metals and on the “taming” of the highly reactive oxygen gas by use of micro-flow reactors and membranes. A useful reference for industrial and academic chemists working on oxidation processes, as well as green chemists.

The field of organometallic chemistry has emerged over the last twenty-five years or so to become one of the most important areas of chemistry, and there are no signs of abatement in the intense current interest in the subject, particularly in terms of its proven and potential application in catalytic reactions involving hydrocarbons. The development of the organometallic/ catalysis area has resulted in no small way from many contributions from researchers investigating palladium systems. Even to the well-initiated, there seems a bewildering and diverse variety of organic reactions that are promoted by palladium(II) salts and complexes. Such homogeneous reactions include oxidative and nonoxidative coupling of substrates such as olefins, dienes, acetylenes, and aromatics; and various isomerization, disproportionation, hydrogenation, dehydrogenation, car bonylation and decarbonylation reactions, as well as reactions involving formation of bonds between carbon and halogen, nitrogen, sulfur, and silicon. The books by Peter M. Maitlis - The Organic Chemistry of Palladium, Volumes I, II, Academic Press, 1971 - serve to classify and identify the wide variety of reactions, and access to the vast literature is available through these volumes and more recent reviews, including those of J. Tsuji [Accounts Chem. Res. , 6, 8 (1973); Adv. in Organometal. , 17, 141 (1979)], R. F. Heck [Adv. in Catat. , 26, 323 (1977)], and ones by Henry [Accounts Chem. Res. , 6, 16 (1973); Adv. in Organometal. , 13, 363 (1975)]. F. R. Hartley's book - The Chemistry of Platinum and Palladium, App!. Sci. Pub!.

The first book to place recent academic developments within the context of real life industrial applications, this is a timely overview of the field of aerobic oxidation reactions in the liquid phase that also illuminates the key challenges that lie ahead. As such, it covers both homogeneous as well as heterogeneous chemocatalysis and biocatalysis, along with examples taken from various industries: bulk chemicals and monomers, specialty chemicals, flavors and fragrances, vitamins, and pharmaceuticals. One chapter is devoted to reactor concepts and engineering aspects of these methods, while another deals with the relevance of aerobic oxidation catalysis for the conversion of renewable feedstock. With chapters written by a team of academic and industrial researchers, this is a valuable reference for synthetic and catalytic chemists at universities as well as those working in the pharmaceutical and fine chemical industries seeking a better understanding of these reactions and how to design large scale processes based on this technology.