The dehydrogenation of saturated organic molecules is utilized for hydrogen production from potential hydrogen energy carriers, and for fundamental oxidation protocols in the manufacture of commodity chemicals. Catalytic dehydrogenative transformations can be divided into: (1) the decomposition of hydrogen storage compounds including formic acid[1–4] and amine–boranes;[5–7] (2) the dehydrogenation of alcohols, amines, and alkanes based on hydrogen-transfer reactions[8–10] with oxidants; and (3) acceptorless oxidation and tandem coupling reactions with hydrogen evolution.
This chapter highlights homogeneous catalysis using transition-metal complexes capable of the dehydrogenation of saturated polar and nonpolar molecules. To emphasize the synthetic utility of dehydrogenated products, this covers the oxidation of alcohols, amines, and simple and functionalized alkanes, but excludes the decomposition of hydrogen
storage compounds. Significant advances in the area of molecular catalysts with metal–ligand cooperation as the key dehydrogenation strategy for the promotion of H+ and H– transfer from polar substrates are discussed (Section 2.4.1), while selected examples of dehydrogenative oxidation in the presence or absence of sacrificial oxidants are
also covered (Section 2.4.2 and Section 2.4.3, respectively). As synthetic applications of catalytic dehydrogenation, oxidative coupling reactions with alcohols are also presented in Section 2.4.3.3.
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