Syntheses of two natural products derived from the ent-kaurene kaurenoic acid are described for the first time using regio-and diastereoselective oxidations. Palladium-and manganese-mediated oxidations were used to accomplish the syntheses of two ent-beyerane metabolites. The use of the White−Gormisky−Zhao catalyst Mn(CF 3 -PDP) enabled the first application of a nondirected metal-catalyzed oxidation in an unactivated C−H bond in a total synthesis.

C―H bond oxidation has arisen as a powerful means for oxygen incorporation in organic molecules. Its use results in fast structural diversification and in a new way of thinking about retrosynthetic disconnections. In this review, we present the application of five metal-catalyzed methodologies for C(sp3)―H oxidation in the total synthesis of natural and unnatural products, covering the period of 2004–2022.

This chapter is an update to Science of Synthesis Section 26.1.2, which included the synthesis of ketones by oxidation of alkanes. This contribution is focused on reports published during the period 2007–2020 that describe the synthesis of ketones by transition-metal catalysis, photochemically and electrochemically mediated methods, as well as the use of supported catalysts and metal-free oxidation of alkanes.